CN1944527A - Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing same - Google Patents

Abstract

The invention provides a thermoset epoxy resin composition of which the viscosity is 5x10<1> - 1x10<4> Pa sec in 50 DEG C and becomes 1x10<6> Pa sec in 1000 seconds in 120 DEG C, further becomes not more than twifold in 50 DEG C after three weeks in 30 DEG C. In addition, the invention provides prepregs for impregnating the thermoset epoxy resin composition, wherein the prepregs has excellent operability and long life in room temperature, keeps good physical properties after forming and is suitable for high speed forming suitable required by industry purpose.

Description

Epoxy resin for prepreg, prepreg, fibre reinforced composites and manufacture method thereof

The application is to be on November 28th, 2003 applying date of original application, and application number is 200380104284.9, and denomination of invention is divided an application for the Chinese patent application of " epoxy resin for prepreg, prepreg, fibre reinforced composites and manufacture method thereof ".

Technical field

The present invention relates to composition epoxy resin, compositions of thermosetting resin, prepreg, fibre reinforced composites and manufacture method thereof.The application's Resins, epoxy is the composition epoxy resin that is suitable for prepreg especially, just can solidify in the lower following short period of time of temperature.Thus, use it can obtain mechanical properties superior prepreg superior, that at room temperature can preserve for a long time.And then compositions of thermosetting resin of the present invention is suitable for high-rate forming, can show high mechanical properties for the fibre reinforced composites (also being recited as FRP among later the present invention sometimes) after being shaped.Thereby, can obtain superior prepreg and formed product of fiber-reinforced composite material by using said composition.Superior prepreg provided by the present invention can be used for obtaining aptly can be as the sheet material of the fibre reinforced composites of the outside plate of transportation means or industrial machine.And then, the method for easily making the superior FRP of high strength and aesthetic appearance, the method for particularly using compression forming method to make with the short period of time are provided among the present invention.

In addition, the application puts down into 14 years No. 346198, Japan's patent application based on Japan's patent application and puts down into 14 years No. 347650, Japan's patent application and put down into 14 years No. 353760, Japan's patent application and put down into 14 years No. 362519, and its content is enrolled among the application.

Background technology

FRP has light weight, high strength, high rigid characters, is widely used to industry purposes such as automobile, aircrafts from motion such as Veronicastrum Herb, golf club and leisure purposes.

Use is the method for prepreg to the intermediate materials of the supporting material impregnated with resin that is made of macrofibers such as fortifying fibres, because the content of control fortifying fibre in prepreg easily, and can design its content high, therefore be suitable as the manufacture method of FRP.

As the concrete grammar that obtains FRP by prepreg, have method, spy that the spy drives the use autoclave that discloses in the flat 10-128778 communique and open the method for utilizing vacuum bag, the spy that disclose in the 2002-159613 communique and open compression forming method that discloses in the flat 10-95048 communique etc.

But, in these any one method, when being heating and curing, under approximately more than or equal to 160 ℃ condition, all need about about 2～6 hours time by solidifying when the lamination prepreg and after with the target shape typing.Promptly need high temperature and processing for a long time.

Yet, can mass production in order to make goods, require just can be shaped in the short period of time to the dozens of minutes in the lower temperature about 100～130 ℃ and at several minutes.Can enumerate for one of method of realizing this problem, use the composition epoxy resin that under a spot of heat, just begins curing reaction, the time method that finishes with the curing of shortening by composition epoxy resin.But if reactive behavior is too high, then curing reaction is out of control easily, and is relatively more dangerous.Yet when using the solidifying agent that in the past adopted, if increase the amount of this solidifying agent, mechanical properties may reduce.And, but such composition epoxy resin is also short between its usage period, at room temperature only preserves and just may solidify in several days.The exploitation that just waiting in expectation like this, at present has the reactive composition epoxy resin of ideal.

Then, if, can enumerate following condition from the desired suitable condition of prepreg is considered.

The drape operability such as (flexibilities) of near the good viscosity room temperature (state is clamminess), appropriateness is superior;

Can keep this operability for a long time, promptly near room temperature, have the long life-span, and then its mechanical properties of FRP and hot rerum natura after being shaped are superior.

Fortifying fibre is soaked into the prepreg that matrix resins such as composition epoxy resin formed, were widely used as the intermediate materials of fibre reinforced composites and can be applied to various fields, but for the situation of above-mentioned industry purposes, the special requirement plasticity is superior.

Now, need about 1 hour being heating and curing for common prepreg, as mentioned above, if comprise the time of the cooling that heats up, then need about 2 or 3 hours～6 hours based on the condition once-forming, its time is very long, becomes one of reason of shaping cost increase.

But if shorten the needed heat-up time that is shaped, then near the life-span room temperature can shorten, and must make the high such disadvantage of forming temperature thereby tend to produce.Giving the exploitation of the compositions of thermosetting resin of prepreg superior characteristic is also carrying out.

Then, characteristic and the FRP sheet material to SMC and prepreg describes.

For the material that is used for FRP beyond the prepreg, be mostly to adopt sheet-shaped moulding material shaped materials such as (hereinafter referred to as SMC) to form.But, in the manufacturing of FRP, use a direction draw neat continuous reinforcing fiber in fact and the prepreg (hereinafter referred to as the UD prepreg) that forms and Fabric prereg etc. use have the SMC in the place that should improve at described several places, back, be favourable aspect the intensity of FRP particularly.

But in order to obtain more superior FRP expeditiously, the prepreg that uses also needs new improvement etc. now.

The sheet material of FRP is because erosion resistance is superior, and just attempting being used as with the automobile is the transportation means of representative and the outside plate of various industrial machines.The FRP sheet material that for example is called SMC is widely used in the engine shield of automobile, splash pan off-grade plate.

SMC (for example opening flat 6-286008 communique with reference to the spy) is the middle base material with mixed pasty states such as the fortifying fibre of the staple fibre of carbon fiber or glass fibre and vibrin.Exert pressure with high pressure to its heating and in mould and (to be generally more than or equal to 50kg/cm ²) and finalize the design, make the base plate that becomes outside plate.Then, cut the surface of this base plate and make it smooth, level and smooth with sand paper or rasion, the covering with paint of painting then, thus form the FRP system outside plate that automobile is for example used.

The outside plate that is formed by SMC is staple fibre (discontinuous fiber) owing to fortifying fibre, thereby with fortifying fibre be continuous fibre situation mutually specific rigidity low (being not only staple fibre is fortifying fibre, the Young's modulus of glass is 70GPa, be low to moderate steel Young's modulus 210GPa 1/3).Thereby the thickness ratio metal outer panel of outside plate is all big, and comparing with metal outer panel sometimes may not light weight, though simultaneously can lightweight also mostly be the situations that alleviate a little.And then SMC system outside plate is discontinuous owing to fiber, thereby low as the intensity of the key property beyond the rigidity of outside plate, is particularly impacted the such local assault of outside plate by sudden thing easily and runs through damage.Thereby, need further to increase thickness for the outside plate that uses outside the room of transportation means etc., perhaps take to paste shock-resistant protection countermeasures such as rubber.Can not be formed on the light weight outside plate that the weight aspect can replace metal system outside plate like this, promptly help the transportation means outside plate of environment.

But the main reason that a lot of outside plates that formed by SMC are practical is by irregularly (roughly even) dispersion of staple fibre, to obtain roughly surface quality uniformly in the base plate before above-mentioned grinding easily.When using continuous fibre, because Fiber Distribution inhomogeneous and inhomogeneous by the complications of fiber, fluctuation, the fiber concavo-convex and thickness that causes such as staggered each other, the surface undulation of base plate is big than staple fibre.Thereby, for this situation, can produce following problem:

1) labour of above-mentioned grinding operation is big;

2) also continuous reinforcing fiber be can grind off during grinding, thereby the machinery and the functional rerum natura of above-mentioned outside plate further reduced.

Yet the situation of continuous fibre has higher rerum natura, and can make the FRP sheet material of light weight, thereby is being ideal aspect rigidity and the intensity.But,, all do not reach practicability though the form of continuous fibre is complicated various to prepreg, fabric, three dimensional fabric etc. for folk prescription.

On the other hand, be that the research of the parts of fortifying fibre is also carried out with the continuous fibre.These parts are made with resin transfer moulding (RTM) etc., this RTM be on mould lamination by the continuous fibre of arranging in one direction and the prepreg of resin formation, be cured with autoclave etc., perhaps the preform with fabric etc. is placed in the mould again, and resin reinjects.But, because the complications of above-mentioned continuous fibre inherent fiber, fluctuation, fiber staggered etc. caused concavo-convex and thickness each other is inhomogeneous, cause surface quality low, actual state is that the outside plate as transportation means such as automobiles does not have practicability.

In order to improve surface quality, adopt the coating method that is called gel coat.So-called gel coat method (opening flat 11-171942 communique with reference to the spy) is that the inner face at mould is pre-formed the resin material coatings such as polyester that can become outer plate surfaces, disposes reinforcing-fiber substrate again on this coating, and close die; Then, inject resin and make its curing, the demoulding is in this coating of surface transfer of FRP outside plate.Present method thereby is of value to industrialization owing to can omit the grinding and the covering with paint on surface.But, when being heating and curing, because the difference of the linear expansivity of FRP and gel coat can produce distortion such as whole molding warpage.Thereby, be not suitable for the outside plate of precision prescribed, and, owing to gel coat breaks or the wrinkling outside plate that is not suitable for.

And then owing to exist concavo-convexly as mentioned above as the surface of the FRP of fortifying fibre with continuous fibre, thereby the thickness of gel coat is thick for the covering with paint films of the situation of covering with paint, lacquer, colour wash, etc. more than or equal to 200 microns.Therefore the defective that exists is, not only weight can increase, and outside plate is subjected to external force and when being out of shape, gel coat can break or peel off, thereby is not suitable for outside plate.

Because the breaking or peel off of gel coat, for the situation of the gel coat of the outside plate that uses without, moisture such as rainwater can be invaded FRP inside, thereby damage light weight, weather resistance as the FRP characteristics sometimes.And the situation of gel coat is compared with covering with paint, and the selection branch of color is few, can't produce the outward appearance that is rich in metal sense and fashion.Thereby the problem of existence is, because the value of whole commodity can reduce, it can not be applicable to the outside plate that automobile exterior panel etc. needs and miscellaneous part is matched colors.Also considered to implement to cover with paint, lacquer, colour wash, etc. on gel coat, further weight increases, cost increases such problem but this situation can produce.

In order to improve surface quality, also carried out other trial (opening the 2001-322179 communique) with reference to the spy by the blanketing fctor of adjusting the carbon fibre fabric that is used as fortifying fibre.

But because carbon fibre fabric is by will be through being processed into intermediate materials, severing lamination preformization, being configured as the so various processing of FRP after weaving, thereby blanketing fctor to be remained on suitable scope be difficult.If by moving of joint filling constraint carbon fiber, blanketing fctor can remain on suitable scope, but because carbon fiber is restrained, the defective of existence is the unusual difficulty of FRP that obtains curve form.

As mentioned above, actual state is to be that fortifying fibre is few in the example of outside plate as the special practicability of FRP sheet material of the prepreg of continuous fibre with having used prepreg, has the structure of the FRP sheet material of practicality, the quantitative target of surface quality is not established.

The linear expansivity of the thickness direction of FRP wants big than metal.Thereby, if the smoothness on surface is poor,, thereby because the lens effect that light such as ultraviolet ray cause, covers with paint, lacquer, colour wash, etc. deterioration and produce spot then because along with the distortion of temperature variation, rainwater etc. can stop, become the outside plate of spot apperance.

The surface quality of outside plate except above-mentioned commodity and long durability, known also can be to producing material impact at the fluid resistance of empty G﹠W.Thereby, be not only automobile, the whole transportation means for electric car, blimp, canoe, boats and ships etc. move are necessary to improve surface quality in order to save the energy.If for lightweight outside plate is made the FRP system usually, then, can produce big distortion at the atmospheric drag that is subjected in the transportation means high-speed mobile because the modular ratio metal is low, resistance to flow can produce bigger variation.Thus, should independently set the standard different at the surface of FRP sheet material with metallic substance.

Repeat, in order to have used the FRP sheet material practicability of continuous fibre, the eager such complex art of quantitative target that requires to establish the structure that is suitable for FRP sheet material, material, surface quality.

Then describe at manufacture method.

As the method that is obtained FRP by shaped material, known as mentioned above have the method for using autoclave, the method for utilizing vacuum bag, a compression forming method etc.Especially, compression forming method is compared with the moulding method of utilizing autoclave and vacuum bag, and curring time is relatively short just can be finished, thus be suitable for having good surface appearance, the mass production of high-intensity FRP.And this method is also easy owing to processing mold, thereby also has the also easy advantage of the FRP that makes complicated shape.

But when using with continuous reinforcing fiber as the shaped material of strongthener by compression molding manufactured FRP, the resin that viscosity reduces is inner or the surface is sharply mobile at FRP because of pressurization.And owing to should flow, the arrangement of fortifying fibre is upset, and produces so-called coil bending.So not only aesthetic appearance can worsen owing to the coil bending of surface portion, and because the arrangement of the fortifying fibre of this part can cause inner coil bending in a jumble, the mechanical properties of FRP can reduce.Therefore, adopt the manufacturing of the FRP of compression forming method to be limited to the situation that the spy opens the use SMC that discloses in the flat 10-95048 communique etc.

Summary of the invention

The result that the inventor carries out lucubrate provides 4 kinds of modes that realize the problem of following record.

One of problem of the present invention provides with composition epoxy resin in the past and compares, even even but also can finish curing at low temperatures in the short period of time and at room temperature preserve the composition epoxy resin that also can guarantee between the sufficient usage period; And, show the fibre reinforced composites of superior mechanical properties according to the prepreg that uses this resin to obtain.It is realized by the first following invention.

It is first mode of the present invention, a kind of composition epoxy resin, it is the composition epoxy resin that is formed by following A composition, B composition, C composition and D composition, and the content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %.

A composition: Resins, epoxy

The B composition: intramolecularly has the resultant of reaction (B-2 composition) that the amine compound (B-1 composition) of at least one sulphur atom and/or Resins, epoxy and intramolecularly have the amine compound of at least one sulphur atom

C composition: urea compounds

D composition: Dyhard RU 100

In above-mentioned composition epoxy resin, can especially preferably use gel time to be composition epoxy resin smaller or equal to 200 seconds at 130 ℃.

In addition, the inventor provides the composition epoxy resin that is associated with first mode, it is the composition epoxy resin that B-2 composition, C composition and D composition by the resultant of reaction of the amine compound that has at least one sulphur atom as Resins, epoxy and intramolecularly constitute, and the content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %.

The B-2 composition: Resins, epoxy and intramolecularly have the resultant of reaction of the amine compound of at least one sulphur atom

C composition: urea compounds

D composition: Dyhard RU 100

And then, the inventor provides the manufacture method of the composition epoxy resin that is associated with first mode, wherein, 100 mass parts A compositions and 0.2～7 mass parts B-1 composition mixed and after obtaining resin combination, further mixed C composition and D composition and when obtaining composition epoxy resin, the content that makes the C composition in the composition epoxy resin is 1～15 quality %.

A composition: Resins, epoxy

The B composition: intramolecularly has the amine compound (B-1 composition) of at least one sulphur atom

C composition: urea compounds

D composition: Dyhard RU 100

Another problem of the present invention provides the compositions of thermosetting resin that is suitable for prepreg, described prepreg except have as the characteristics of in the past prepreg promptly the operability of room temperature and superior in the long lifetime property of room temperature, and can keep shaping after the characteristics of good rerum natura, also have the desired characteristics that can high-rate forming of industry purposes.In addition, provide the prepreg that soaks into this compositions of thermosetting resin and form, and then also provide and use the manufacture method of this prepreg with the superior FRP of high-rate forming machinery intensity and hot rerum natura.

This problem realizes by the second following mode.

Be the application's second mode, a kind of compositions of thermosetting resin, it is to be 5 * 10 50 ℃ viscosity ¹～1 * 10 ⁴Pasec and under 120 ℃ atmosphere, reach 1 * 10 with interior meeting at 1000 seconds or its ⁶The compositions of thermosetting resin of Pasec, its after 30 ℃ were placed for 3 weeks 50 ℃ 2 times of viscosity increases or below it.

The application's another problem be solve used continuous fibre FRP sheet material particularly as the synthtic price index on the structure of outside plate, material, surface.That is, provide following FRP sheet material, it not only has light weight, high rigidity, the high strength that is suitable for transportation means etc., but also has the surface quality that can stand life-time service, has structure, material, the superficiality of the outside plate that is of value to the FRP of environment system.This problem realizes by following Third Way.

Be the application's Third Way, (1) with compacting pressure more than or equal to 10kg/cm ², curring time is the prepreg smaller or equal to 0.5 μ m at the center mean roughness (Ra) on the surface of 15 minutes or its FRP sheet material that obtains with interior being heating and curing; (2) with compacting pressure more than or equal to 10kg/cm ², curring time is at 15 minutes or its FRP sheet material that obtains with internal heating curing, it is that the center mean roughness (Ra) on the surface of FRP sheet material is the FRP sheet material smaller or equal to 0.5 μ m.

Another problem of the present invention makes high strength at short notice by compression forming method and aesthetic appearance is superior, with continuous reinforcing fiber in fact as the FRP of strongthener.This problem realizes by following mode.

Be the application's cubic formula, a kind of manufacture method of formed product of fiber-reinforced composite material is characterized in that, comprises the steps: in advance the shaping dies temperature adjustment to the solidification value of thermosetting resin or the step more than it; (monoplanar surface is amassed S in this thermoregulated shaping dies ₂) put into to continuous reinforcing fiber in fact soak into thermosetting resin and the shaped material that forms (monoplanar surface is amassed S ₁) step; Closed subsequently shaping dies makes shaped material be full of the step of whole shaping dies inside; Compression molding is so that S ₁/ S ₂It is 0.8～1 step.

Description of drawings

Figure 1A is that expression has been placed the sectional view of the state of shaped material at mould inside before the close die;

Figure 1B is the sectional view of the state of expression close die;

Fig. 2 is a sectional view of representing preferably to be used to the total marginal texture of the part mould that uses in the cubic formula of the present invention, that upper die and lower die (formpiston and former) contact during close die;

Fig. 3 is a sectional view of representing preferably to be used to the hole to be opened/closed mould, that be located at mould inside of using in the cubic formula of the present invention.Also can be used in the demoulding of FRP by blowing from this hole.

Embodiment

Below be described in detail at the cubic formula of first mode to the of the present invention.

First mode

Following explanation first mode of the present invention, the prepreg that obtains at each composition and additive, manufacture method and then by Resins, epoxy etc. is described in detail.

Provide following composition epoxy resin by the manner, itself and composition epoxy resin in the past compare, even also can finish curing in the short period of time at low temperatures, even and at room temperature preserve and also can guarantee the sufficient serviceable time.According to the prepreg that uses this resin to obtain, can obtain showing the fibre reinforced composites of superior mechanical properties.

(A composition)

A composition in first mode is a Resins, epoxy.As its example, two functionality Resins, epoxy can be enumerated the Resins, epoxy behind these materials of bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin or modification etc.Example as trifunctional or the multi-functional Resins, epoxy more than it, can enumerate the brominated epoxy resin after the such Racemic glycidol ether type epoxy of such glycidyl amine type epoxy resin, four (the glycidyl oxygen phenyl) ethane and three (glycidyl oxygen methylmethane) of phenolic resin varnish type epoxy resin, cresols type Resins, epoxy, four Racemic glycidol diaminodiphenylmethane, triglycidyl group amino-phenol, four glycidyl amines and Resins, epoxy, bromination behind these materials of modification are handled these Resins, epoxy, but be not limited to this.In addition, as the A composition, also these Resins, epoxy combinations can be used more than a kind.

Especially, can especially preferably use bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, cresols varnish type Resins, epoxy.If these Resins, epoxy are compared with the situation of for example using intramolecularly to have the high Resins, epoxy of the rigidity such as Resins, epoxy of naphthalene skeleton, the effect of the physical strength in the time of can playing further raising and make molding.This be because, if the high Resins, epoxy of rigidity is solidified at short notice, then because cross-linking density increase is easy to generate strain, on the contrary, if use above-mentioned Resins, epoxy, the possibility that then produces such problem is low.

On the other hand, have the Resins, epoxy of sulphur atom, bisphenol-s epoxy resin is arranged and have the Resins, epoxy of sulphur skeleton, also they can be used for the present invention as intramolecularly.But, in the present invention,, need the content of the sulphur atom in the composition epoxy resin be carried out quantitatively in order to use these materials effectively.Method for the content of the sulphur atom in the prior quantitatively composition epoxy resin can be used atomic absorption spectrometry etc.

(B composition)

The B composition of first mode is the resultant of reaction (B-2 composition) that the amine compound (B-1 composition) of intramolecularly with at least one sulphur atom and/or Resins, epoxy and intramolecularly have the amine compound of at least one sulphur atom.

The B-1 composition is so long as intramolecularly has the amine compound of at least one sulphur atom just is not particularly limited, for example preferably use 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diamino-diphenyl sulfide, two (4-(4-amino-benzene oxygen) benzene) sulfone, two (4-(3-amino-benzene oxygen) benzene) sulfone, 4,4 '-diamino-diphenyl sulfide, o-tolidine sulfone, and the derivative of these materials etc.

On the other hand, the B-2 composition is the resultant of reaction of amine compound reaction with at least one sulphur atom of above-mentioned Resins, epoxy and intramolecularly.In the composition epoxy resin of the manner, by mixing A composition and B-1 composition and make its reaction can obtain containing the B-2 mixture of ingredients, but do not need specially from wherein isolating the B-2 composition separately.

In addition, in the process of the composition epoxy resin of making the manner, the some or all of of material that adds as A composition and B-1 composition can be changed to the B-2 composition.

At this moment, one in A composition and the B-1 composition or both can all be consumed and be changed to into the B-2 composition.

In the manner, can use any of B-1 composition and B-2 composition, but when being to use B-2 composition or B-1 composition and B-2 mixture of ingredients, can improve storage stability.

(C composition)

C composition in the manner is a urea compounds.

The C composition is not particularly limited, but the preferred urea compounds such as dichloro-dimethyl urea, phenyl dimethyl urea that use.Especially, do not have the material of halogen atom at intramolecularly, it is reactive high and toxicity is also low, thereby can be suitable for as C composition especially.

Can also contain the amide of carbonic acid, carbamic amide among the present invention in the said urea compounds.Generally can make phosgene, chloro-formic ester, hydrargyrum amidochloratum formyl, carbonic ether, isocyanic ester, cyanic acid etc. and the amine of ammonia etc. be used for obtaining.

The compound that alkane urea (alkyl urea) that makes uride (acylurea) that urea and acyl chlorides effect obtain and obtain with the hydrogen of alkyl substituted ureas etc. is commonly referred to the urea class is also contained in the manner in the said urea compounds.

In addition, said urea compounds also comprises urea complex in the manner.

If urea complex is enumerated an example and described, then be meant at the saturated solution of lower alcohols such as the saturated aqueous solution of hydrocarbon mixture and urea or methyl alcohol and imported the material of hydrocarbon in the crystalline texture of the urea that obtains.

The content of the C composition in the composition epoxy resin need be 1～15 quality %.Be preferably more than and equal 3 quality %, and be preferably smaller or equal to 12 quality %.If less than 1 quality %, then curing reaction can fully not finished sometimes; If surpass 15 quality %, but then short between the usage period, near room temperature, possibly can't preserve for a long time.

And then when using the solid material as the C composition, median size is preferably smaller or equal to 150 μ m, more preferably smaller or equal to 50 μ m.If median size surpasses 150 μ m,, might can't realize the i.e. curing at short notice of most important effect of the present invention then because dispersion of particles speed reduces, and consequently the speed of curing reaction reduces.

(D composition)

D composition in first mode is a Dyhard RU 100.This Dyhard RU 100 plays the effect of curing agent for epoxy resin, by with the manner in other compositions be used in combination can be in lower temperature-curable.

In the manner, the content of the D composition in the composition epoxy resin is preferably 0.1～10 quality %.In addition, if the median size of D composition smaller or equal to 150 μ m, particularly smaller or equal to 50 μ m, favorable dispersity then, speed of response accelerates, thereby is preferred.

(other additives)

In the composition epoxy resin of first mode, can also add in right amount micronized inorganic particles such as silica, pigment, elastomerics, as the aluminium hydroxide of fire retardant and bromide or phosphorus series compound, deaerating agent, with improve the such thermoplastic resin that is dissolved in Resins, epoxy of polyvinyl acetal resin that operability and flexibility are purpose and phenoxy resin, as imdazole derivatives, metallic complex salt or the tertiary amine compound etc. of the catalyzer of curing reaction.

(content of the sulphur atom in the composition epoxy resin)

In the composition epoxy resin of first mode, the content of the sulphur atom in the composition epoxy resin is necessary for 0.2～7 quality %.If less than 0.2 quality % then is difficult to finish curing in the short period of time at low temperatures; If surpass 7 quality %, but then might shorten between the usage period.

(gel time)

The composition epoxy resin of first mode is smaller or equal to 200 seconds at 130 ℃ gel time preferably.In the manner, when so-called gel time is meant the temperature that raises specific to uncured composition epoxy resin, by the time of finishing gelation.At this, so-called gelation is meant the state that composition epoxy resin loses flowability at intermolecular formation three-dimensional net structure.

At the composition epoxy resin of 130 ℃ gel times, especially can realize at short notice solidifying smaller or equal to 200 seconds.

(manufacture method of composition epoxy resin)

The manufacture method of the composition epoxy resin of the manner for example can be added above-mentioned A composition, B-1 composition, C composition, D composition and other additive and mixing in right amount.At this moment, as mentioned above, the A composition of interpolation and part or all reaction of B-1 composition and to be changed to the B-2 composition also passable.

And, also can be pre-mixed A composition and B-1 composition, after modulation contains the resin combination of B-2, remix C composition and D composition.

In addition, the temperature during mixing is preferably 50～180 ℃, more preferably 60～160 ℃.

(prepreg)

By being impregnated in the fortifying fibre as matrix resin, obtain the prepreg that can be shaped at short notice in lower temperature with above-mentioned composition epoxy resin.The manufacturing of prepreg can be undertaken by known device and manufacture method.

The fortifying fibre that can be applicable to first mode can use various fibers according to the application target of matrix material, is not particularly limited.For example preferably use carbon fiber, graphite fibre, Kevlar, silicon carbide fiber, sapphire whisker, boron fibre, wolfram varbide fiber, glass fibre etc.And, can be used in combination these multiple fortifying fibres.

In these fortifying fibres, carbon fiber and graphite fibre because better than Young's modulus, lightweight is had important result, thereby be suitable for the present invention.In addition, can use the carbon fiber and the graphite fibre of all kinds, but special preferred tensile strength be to be more than or equal to 190GPa more than or equal to 3500Ma, modulus in tension according to purposes.

In addition, being not particularly limited as the form of the fortifying fibre in the prepreg, can be that fortifying fibre is drawn the form of neat form and braiding or used the non-woven fabrics of cutting out short fortifying fibre etc. in a direction.Particularly draw the situation of the form of neat form and braiding in a direction, so far by being configured as of compression forming method, if spended time, then resin can flow in mould, thereby can not get the good fibre reinforced composites of outward appearance by solidifying.But,, then solidify at short notice, thereby can obtain the good fibre reinforced composites of outward appearance owing to composition epoxy resin if use the composition epoxy resin of the manner.

Second mode

Below describe at second mode of the present invention, that has at length put down in writing each specifies preferred example with the manner etc.

By second mode, the superior compositions of thermosetting resin that is suitable for prepreg is provided, described prepreg is in the operability of room temperature and superior in the long lifetime property of room temperature, and when keeping good rerum natura after the shaping, can carry out the desired high-rate forming of industry purposes.

[mensuration of viscosity]

The inventor carries out the result of lucubrate in order to solve above-mentioned problem, confirmed compositions of thermosetting resin viscosity, heated condition (being specially 120 ℃) arrive target viscosities time, and place after viscosity be important.In second mode, the mensuration of viscosity uses the RDS-200 that Rheometrics company makes (the dynamic viscosity determinator with equal performance also can) to carry out, and the value that obtains is to use the value of the parallel plate of 25mm φ with the frequency measurement of 1Hz.Intensification condition to the temperature of heated condition (being specially 120 ℃) describes in detail in its part.

[50 ℃ viscosity is 5 * 10 ¹～1 * 10 ⁴Pasec]

The compositions of thermosetting resin of second mode need be 5 * 10 50 ℃ viscosity ¹～1 * 10 ⁴Pasec.

In this viscosity less than 5 * 10 ¹During Pasec, near the viscosity when making prepreg room temperature is strong excessively, can become to be very difficult to operation.On the contrary, this viscosity surpasses 1 * 10 ⁴During Pasec, the drape of prepreg will disappear and become hard, still become to be difficult to operation.

[under 120 ℃ atmosphere, reach 1 * 10 with interior at 1000 seconds or its ⁶Pasec]

Then, compositions of thermosetting resin must reach 1 * 10 at 1000 seconds or its with interior at 120 ℃ in second mode ⁶Pasec.

Reach 1 * 10 by viscosity ⁶The time of Pasec is when surpassing 1000 seconds, and is long at the pyritous curring time.In the time of in 800 seconds or its, because short, thereby be preferred at the pyritous curring time, more preferably 600 seconds or it is with interior situation.

Measuring method uses in the method described in [mensuration of viscosity], is following enforcement to the intensification condition of the temperature of heated condition (being specially 120 ℃).That is, after 50 ℃ of stationary heat thermosetting resin composition sample, be warming up to 120 ℃, and measure isothermal viscosity at 120 ℃ with 10 ℃/minute heat-up rates.The time point that reaches 120 ℃ from temperature picks up counting, to reaching 1 * 10 by viscosity ⁶The time of Pasec is carried out timing.By 1 * 10 ⁶The viscosimetric analysis of Pasec can be measured minimum by 1 * 10 at need ²Viscosity about Pasec, 2 last points of extrapolation are calculated and are reached 1 * 10 ⁶The time of Pasec.Even but minimumly also need to implement 1 figure place or the above viscosimetric analysis of 1 figure place.That is to say, by being inserted in 1 * 10 outward ²The data of Pasec obtain 1 * 10 ⁶During the viscosity of Pasec, the viscosity when arriving 120 ℃ must be smaller or equal to 1 * 10 ¹Pasec.

[placing 3 all backs 50 ℃ 2 times of viscosity increases or below it] at 30 ℃

And, the compositions of thermosetting resin of second mode 30 ℃ place 3 week the back be necessary for 2 times or below it 50 ℃ viscosity increases.

The measuring method of viscosity is identical with [mensuration of viscosity].This viscosity increases when surpassing 2 times, near the bad stability of prepreg room temperature.

[resin composition]

Raw material as the compositions of thermosetting resin of second mode, be not particularly limited, can illustration Resins, epoxy, resol, vinylester resin, unsaturated polyester resin, bimaleimide resin, bismaleimide-triazine resin, cyanate ester resin, benzoxazine colophony, acrylic resin etc., but consider from operability, cured article rerum natura, preferred Resins, epoxy, bimaleimide resin, bismaleimide-triazine resin, the cyanate ester resin of using, especially the binding property of Resins, epoxy and supporting material is superior, thereby especially preferably uses.

For rerum naturas such as the operability that improves prepreg, the outward appearance that improves the FRP after being shaped and raising shock-resistance, also can add thermoplastic resin and other additives in the compositions of thermosetting resin of the manner.

Make an addition to the thermoplastic resin in second mode as suiting, can enumerate as aromatic poly, polyester, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polyarylester, polyimide, polyetherimide, polysulfones, polymeric amide, polyamidoimide, polyether-ether-ketone etc.

In addition, as other additive, can enumerate as natural rubbers such as synthetic rubber such as elastomeric isoprene-isobutylene rubber, polyisoprene rubber, paracril, silicon rubber and latex etc.

[interpolation of filler]

For the surface smoothing that makes the FRP that obtains is good, the preferred weighting material such as filler that adds in the compositions of thermosetting resin of second mode.As the preferred lime carbonate of filler, preferred 3～10 μ m of the particle diameter of lime carbonate.

The addition of filler because of the kind of the resin of compositions of thermosetting resin is different, but is 10～300 mass parts with respect to 100 mass parts compositions of thermosetting resin preferably.

In addition, needless to say, add the situation of aforesaid additive in the compositions of thermosetting resin of the manner, the compositions of thermosetting resin that finally is impregnated into prepreg also must satisfy above-mentioned viscosities.

[prepreg]

The prepreg of second mode is compositions of thermosetting resin of the present invention to be impregnated into supporting material and the prepreg that forms.The material of the supporting material that uses in the prepreg as the manner is not particularly limited, can enumerate as carbon fiber, glass fibre, Kevlar, high-strength polyethylene fiber, boron fibre, steel fiber etc., but preferred use can obtain the performance of superior FRP, particularly light weight and high strength, the carbon fiber of high inflexible mechanical properties, glass fibre.

The form of the supporting material that uses in the prepreg as second mode also is not particularly limited, can enumerate as to a direction or change angle and lamination plain goods, twilled fabric, satin and sateen cloth or the fibrous bundle object of state sew up, make its can be not unfolded sutural lamina as not having crooked fabric (non-crimpfabric) or non-woven fabrics, shim-like object, also have a direction draw neat fortifying fibre and the folk prescription that forms to material etc., but preferred superior fabric or the sutural lamina of operability that use.

The resin content of the prepreg of the manner is not particularly limited, but resin content is few more, and the outward appearance of the FRP that obtains is good more, and the reinforcing effect of supporting material is big more, thereby is preferred.Specifically, the volume content of the compositions of thermosetting resin in the prepreg is preferably smaller or equal to 45 volume %, more preferably smaller or equal to 40 volume %, is preferably especially smaller or equal to 35 volume %.

Lower limit about the volume content of the compositions of thermosetting resin in the prepreg if the content of compositions of thermosetting resin is very few, then can produce the situation that compositions of thermosetting resin can not be filled into each corner of FRP, so bad.Specifically, the content of compositions of thermosetting resin is preferably more than and equals 20 volume %, more preferably more than or equal to 25 volume %.

[manufacture method of FRP]

The manufacture method of the FRP of second mode is that the prepreg with the manner is placed in the shaping dies manufacture method of the FRP that close die heats, pressurizes and is shaped.Be not particularly limited as shaping dies, even but metal shaping dies also is difficult to distortion because it applies high pressure, thereby be preferred.

Temperature for heating also is not particularly limited, but high temperature can shorten curring time more, thereby is preferred.Be preferably more than specifically and equal 120 ℃, more preferably more than or equal to 140 ℃.But, if temperature is too high, then reduce the temperature of shaping dies will be very spended time, perhaps do not reduce temperature and when placing prepreg, owing to begin to solidify, resin does not arrive each corner of final shaping thing sometimes.Therefore heating is preferably smaller or equal to 200 ℃, more preferably smaller or equal to 180 ℃.Degree for pressurization also is not particularly limited, but the situation of carrying out high-pressure forming can reduce the pin hole on surface and the space of FRP inside, thereby is preferred.Specifically, the pressure that puts on prepreg is preferably more than and equals 0.5MPa, more preferably more than or equal to 1MPa.On to be limited to 100MPa then enough.

Have no particular limits for the equipment, the pattern that are shaped, but be to use its efficient of method of heating and pressurizing equipment of hydraulic type best, be suitable for the manufacture method of FRP of the present invention.The shaping dies that preferably has the enclosed system of common edge structure for the shaping dies of this moment.

Third Way

Below describe at Third Way of the present invention.

In the Third Way, provide can solve used continuous fibre FRP sheet material particularly as the superior prepreg and the FRP sheet material of the synthtic price index on the structure of outside plate, material, surface.

＜prepreg 〉

[compacting pressure]

For the prepreg of Third Way, for center line average roughness (Ra) with FRP sheet material smaller or equal to the surface of good quality of 0.5 μ m and have the surface quality that can stand life-time service, need be with more than or equal to 10kg/cm ²Compacting pressure be shaped and continuous reinforcing fiber in fact soaked into the prepreg of matrix resin.

Insufficient pressure 10kg/cm during shaping ²The time, be difficult to form the surface of good quality.

[curring time]

In Third Way, in order to obtain being used for the FRP sheet material of the extra high transportation means purposes of cost consciousness, need be that 15 minutes or its are heating and curing with interior at curring time, and then be preferably 10 minutes or its in.In the present invention, so-called curring time is meant that prepreg is placed on the time of the state that applies the shaping temperature and pressure.

[fortifying fibre]

The fortifying fibre that can use in Third Way is so long as continuous reinforcing fiber in fact, and its kind just is not particularly limited, and can use carbon fiber, glass fibre, Kevlar, trevira, boron fibre etc.Wherein, as the parts of flyer and automobile etc., can use the specific tenacity carbon fiber higher by optimum than elasticity.

The form of the fortifying fibre in the shaped material can use a direction draw neat fortifying fibre form, woven the form of fortifying fibre etc., be not particularly limited.For example, in order to improve the aesthetic appearance of FRP, the shaped material on the surface of the FRP fabric with fortifying fibre can be strengthened, neat fortifying fibre etc. is then drawn in a direction in inside, and with a plurality of enhancing forms.

In addition, in this manual, so-called continuous reinforcing fiber in fact is meant the fiber that does not have the end in the inside of shaped material in fact.

In the prepreg of the manner, preferably use carbon fiber as fortifying fibre.Carbon fiber can use any that PAN (vinyl cyanide) is, pitch is.The carbon fiber of PAN system is considered from the balance aspect of intensity, Young's modulus, elongation, and is more preferred aspect the making fabric.As the outside plate purposes, intensity and Young's modulus are high more unreasonablely to be thought, but in order to make it have shock-resistance, preferred elongation is the carbon fiber more than or equal to 1.4%.The elongation of FRP is obtained according to JIS K-7054, thereby is meant the tension fracture strain strictly speaking.

[carbon fibre fabric]

Carbon fibre fabric forms fabric shapes such as plain goods, twilled fabric, satin and sateen cloth with the continuous fibre state.Wherein, the mass area ratio (Wg/m of the preferred carbon fibre fabric of fabric among the present invention ²) with the ratio (W/t) of thickness (tmm) in 700～1700 scope.

The fabric that is in this scope is called flimsy material, and is thinner by mass area ratio, has the structure of fiber diffusion.Because the fluctuating of the thickness direction of fiber is little, it can show high intensity and rigidity, makes outside plate lightweight more.And because fabric face concavo-convex little, thereby the surface quality of outside plate also improves, and the weather resistance of FRP sheet material also can improve.In addition, the mass area ratio of fabric and thickness are measured according to JIS R7602.

And then, when the blanketing fctor of carbon fibre fabric is in 90～100% the scope, only few by the part of resin formation, face impacts characteristic outward when uprising, resin shrinks and the concave-convex surface or the concavo-convex spot that cause disappear to thickness direction, obtains high mapping boldness, from but preferred.In running through impact, if also the sudden thing of imagination is the situation of small pieces, then preferred blanketing fctor is in 95～100% the scope.

The blanketing fctor Cf of carbon fibre fabric, opening flat 7-118988 communique as the spy puts down in writing, defines, be the key element relevant with the size that is formed on the space part between textile yarn, when on fabric, setting area S regional, if the area that is formed on the space part between yarn for weaving purpose in the area S is set at s, it is meant the value by the following formula definition.

Blanketing fctor Cf (%)=(S-s)/S} * 100

In addition, because this fabric helps the surface rigidity and the surface quality of particularly important in the rerum natura of outside plate, thereby the optimum seeking site of this fabric is near the upper layer of plate.Have high inflexible carbon fiber by the top layer at outside plate, the surface rigidity of outside plate further improves, and lightweight becomes possibility.

Most preferred position is an outermost layer.And, if twin shaft to or three axially etc. multi-axial fabric be in outermost layer, then can also give the appearance of fabrics of outside plate uniqueness.And then the fabric that ties up to above-mentioned scope by the pass that makes mass area ratio and thickness is positioned at outermost layer, and it is very level and smooth that the surface of outside plate becomes, and is also very level and smooth when being provided with thin filming.

That is mass area ratio (the Wg/m of carbon fibre fabric, ²) be in above-mentioned flimsy material in 700～1700 the scope with the ratio (W/t) of thickness (tmm), because concavo-convex, tortuous little along the thickness direction of fiber, thereby the variation in thickness of the resin layer on surface is little when making outside plate, can obtain more level and smooth surface before covering with paint, lacquer, colour wash, etc., after covering with paint, lacquer, colour wash, etc.

In addition, if blanketing fctor is in 90～100% the scope, then the thickness direction at outside plate does not have the place that only is made of resin, thereby this characteristic very important aspect weather resistance of mapping boldness is improved, practicality increases, thereby is preferred.

[fortifying fibre beyond the carbon fiber]

Among the present invention, except carbon fiber, can also and use organic fibres such as inorganic fibre, aromatic poly series fiber and nylon such as glass fibre, sapphire whisker, silicon nitride fiber.Macrofiber, staple fibre, textile-like, the object of shim-like or the mixture of these forms etc. by dispose them regularly or brokenly in carbon fiber or resin can improve shock-resistance, shock absorbing characteristics etc.

Especially, its low price of glass fibre, compression/tensile strength balance is good.Glass fibre is meant with silicon-dioxide (SiO ₂) as fibrous glass such as the so-called E glass of principal constituent, C glass, S glass, the optimum fiber diameter is the glass fibre about 5～20 μ m.Woven fiber glass can keep resin, thereby plasticity is good improving inflexible simultaneously.Suitable is that Measurement of Quality in Unit Area of Fabric is 20～400g/m ²Woven fiber glass.When being used for the top layer, if be 20～50g/m ², then can not damage the aesthetic appearance of fabric, and also can keep the transparency, thereby be preferred.

The consumption of glass fibre, when needing rigidity preferably smaller or equal to 50 weight % of carbon fiber, when needing shock-resistance preferably smaller or equal to 80 weight %.

In addition, organic fibre and be fragility unlike carbon fiber and glass fibre, but toughness, it is a disturbing property, even have the crooked such characteristics that rupture that also are not easy.And synthon and carbon fiber be relatively the time and since have not can electrocorrosion like this, thereby it has the advantage that does not need the electrocorrosion countermeasure such.

Moreover, when organic fibre and glass fibre compare, owing to can burn, thereby have easily discarded such advantage; And then because proportion is the only about half of of glass fibre, thereby also has and to make the extremely such advantage of lightweight of parts.

[matrix resin]

The resin that constitutes the FRP sheet material of Third Way comprises thermosetting resin such as Resins, epoxy, vinylester resin, unsaturated polyester resin, resol, benzoxazine colophony, acrylic resin and these resins of modification and the modified resin that obtains.

Wherein, the modified resin of Resins, epoxy, vibrin, vinylester resin and these resins that preferred resistance to chemical reagents, weathering resistance etc. are superior.In addition, resol, its flame retardant resistance of benzoxazine colophony are superior, are preferred for requiring stable on heating outside plate.

Moreover transparent resins such as acrylic resin are preferred aspect aesthetic appearance.Wherein, its weathering resistance of acrylic resin is superior, thereby is preferred.And then, by in these transparent resins, adding 3～20% UV light absorber or sunlight absorption agent, oxidation inhibitor, can further improve weathering resistance.

[resin combination (1)]

And then, can enumerate composition epoxy resin as first mode of the present invention (with reference to the record of first mode, below be recited as resin combination (1) sometimes) as the preferred matrix resin that uses in the Third Way.In addition, short of specific questions such as the material of putting down in writing in the resin combination of first mode, condition and preferred example also are preferred in Third Way.

When using this resin combination (1), can solidify at short notice in lower temperature, thereby use this composition epoxy resin and even but the prepreg that obtains is at room temperature preserved and also had between the sufficient usage period, and show superior mechanical properties by the FRP sheet material that this prepreg obtains.And then, by using this prepreg, in the shaping of fibre reinforced composites, can shorten process period, thereby can low-costly make.

(other additives)

In resin combination (1), can use and the same additive described in first mode.

(content of the sulphur atom in the resin combination (1))

Resin combination (1) can have with first mode in the content of the same sulphur atom put down in writing.

(gel time)

Resin combination (1) preferably has the gel time same with first mode.

(manufacture method of resin combination (1))

Resin combination (1) can be used and the same method manufacturing of first mode.Optimum condition in first mode is preferred too in Third Way.

(prepreg)

In Third Way and first mode same, can be impregnated into above-mentioned resin combination (1) in the fortifying fibre as matrix resin and obtain.The kind of fortifying fibre and form etc. also can be used with first mode same, and preferred example is similarly preferred.

Form as the fortifying fibre in the prepreg is not particularly limited, and can be fortifying fibre is drawn neat form and by the form that woven or use the non-woven fabrics of cutting out short fortifying fibre etc. in a direction.Particularly draw neat form and by the situation of the form that woven in a direction, being configured as by compression forming method in the past, if by solidifying spended time, then resin can flow in mould, thereby can not get the good fibre reinforced composites of outward appearance, still, if use the composition epoxy resin of the manner, then can solidify at short notice, thereby can obtain the good fibre reinforced composites of outward appearance owing to composition epoxy resin.

As above detailed description, resin combination (1) can solidify at short notice in lower temperature.Thereby, even use this composition epoxy resin and but the prepreg that obtains is at room temperature preserved and also had between the sufficient usage period, and show superior mechanical properties by the matrix material that this prepreg obtains, can access such effect.And then, by using this prepreg, in the shaping of fibre reinforced composites, can shorten process period, thereby can low-costly make.

[resin combination (2)]

Also have, the preferred matrix resin that uses in the prepreg of Third Way, if consider from its curing characteristics, it also is preferred then using the compositions of thermosetting resin (with reference to second mode, below be recited as resin combination (2) sometimes) of the application's second mode.In addition, short of specific questions such as the material of putting down in writing in the resin combination of second mode, condition and preferred example also are preferred in Third Way.

This compositions of thermosetting resin suitable as maintain the operability of room temperature, in long lifetime of room temperature and in the good rerum natura after being shaped, can carry out the matrix resin of the prepreg of the desired high-rate forming of industry purposes.And, prepreg maintain the operability of room temperature, in long lifetime of room temperature and in the good rerum natura after being shaped, can carry out the desired high-rate forming of industry purposes, therefore can carry out the desired high-rate forming of industry purposes.

Then, explain at resin combination (2).

(mensuration of viscosity)

Similarly measure with second mode.

(50 ℃ viscosity is 5 * 10 ¹～1 * 10 ⁴Pasec)

With the explanation in second mode be same.

(under 120 ℃ atmosphere 1000 seconds its reach 1 * 10 with interior ⁶Pasec)

With the explanation in second mode be same.

(placing 3 all backs in 2 times of the increases of 50 ℃ viscosity or below it) at 30 ℃

With the explanation in second mode be same.

(resin composition)

Can use the resin of putting down in writing in second mode to form equally.

(interpolation of filler)

Can use the record in second mode equally.

(prepreg)

Can similarly make according to the record in second mode.Preferred example such as amount and material is preferred too in Third Way in second mode.

(manufacture method of FRP)

Can similarly in Third Way, make FRP with second mode.In second mode, preferably create conditions and examples such as method, equipment in Third Way too for preferred.

Resin combination (2) can provide suitable as maintain the operability of room temperature, in long lifetime of room temperature and in the good rerum natura after being shaped, can carry out the compositions of thermosetting resin of matrix resin of the prepreg of the desired high-rate forming of industry purposes.

And, the prepreg that obtains by resin combination (2) maintain the operability of room temperature, in long lifetime of room temperature and in the good rerum natura after being shaped, can carry out the desired high-rate forming of industry purposes.And then, can carry out the desired high-rate forming of industry purposes.Resin combination (2) is very suitable for high-rate forming, the shaping process cost of minimizing as the greatest drawback of FRP of going a long way greatly.

[ratio of the matrix resin in the prepreg]

The ratio of the matrix resin in the prepreg preferably is in 20～45% the scope by quality ratio.This be because, then similar if surpass 45% for the rigidity, shock-resistance and the metal system outside plate that make the FRP flat board, the lightweight of might having to sacrifice.

In addition, the reason more than or equal to 20% be because, if less than 20%, then matrix resin soak into the difficulty that becomes, produce to the crack and may be bad aspect the rerum natura.

The ratio of the matrix resin in the prepreg is 20～30%, when using Resins, epoxy as matrix resin, also can obtain sufficient flame retardant resistance even do not add fire retardant in Resins, epoxy, thereby be preferred.

[surfaceness-center mean roughness (Ra)]

Its center mean roughness (Ra) with the surface of the above-mentioned resulting FRP of molding condition of the prepreg of the manner is smaller or equal to 0.5 μ m, and this low and low aspect of weather resistance for the concavo-convex outward appearance that causes of FRP plate surface is necessary.Center mean roughness (Ra) is more preferred during smaller or equal to 0.5 μ m.Concavo-convexly can not eliminate by covering with paint, lacquer, colour wash, etc., can be more remarkable.And, not only damage outward appearance, corresponding its size can become greatly at the vertical stress concentration of recess, destroy thereby advance, thereby concavo-convex little situation can improve the weather resistance of outside plate.

In the manner, the roughness tester 178-368 (resolution unit 178) that the center mean roughness (Ra) on FRP surface is to use Japanese Mitsutoyo K.K. to make, with intercepting value: 2.5mm, measure interval: 2.5 * 5mm, scope: 5 μ m measure.Certainly, the FRP surface produces caused by the damage of metal die face concavo-convex sometimes, thereby will be with except such part and measure in above-mentioned mensuration.

[manufacturing process]

The prepreg of the manner for example is cured by following, can obtain the FRP flat board.

To have in advance when close die from mould inside can eluting gas but can suppress the effusive structure of resin, surface accuracy for more than or equal to the mould temperature adjustment of #800 to the solidification value of compositions of thermosetting resin or more than it, in this mould, put into the laminate of the above-mentioned prepreg that constitutes by the successive carbon fiber, close die makes the laminate of prepreg be full of the whole inside of mould and compression molding then.

And " can the eluting gas from mould inside when close die but can suppress the effusive structure of resin " that mould has generally can be enumerated the structure and the rubber sealing structure that are called as the common edge structure.

In addition, mould preferably has when close die or can make the structure of the inner degassing during just in close die.

As this degassing structure, have at mould inside hole to be opened/closed is set, it is open in the mould outside, is communicated with above-mentioned hole and with the container of pump to the inside degassing, opens valve when close die is inner, with methods such as mould inside one qi exhaustion gas by valve.

And then, after the shaping of FRP sheet material finishes,, also the mechanism with the demoulding of FRP sheet material such as ejector pin and air valve can be installed on mould in order to take out FRP sheet material easily.Thus, do not wait mold cools down just can easily take out FRP sheet material, thereby be suitable for mass production.In addition, the mechanism of the demoulding can be ejector pin, air valve or mechanism in addition, also can be known in the past any mechanism.

With S ₁/ S ₂Be that (monoplanar surface is long-pending to be S in this mould for 0.8～1 state ₂) (monoplanar surface is long-pending to be S to put into the laminate of the above-mentioned prepreg that is made of continuous carbon fibre ₁), depress can be extremely not mobile adding for matrix resin, thereby be preferred.The mobile meeting of matrix is flowed fortifying fibre, thereby it is concavo-convex that the FRP plate surface is produced.Concavo-convexly can not eliminate by covering with paint, lacquer, colour wash, etc., can be more remarkable.And, not only damage outward appearance, corresponding its size can become greatly at the vertical stress concentration of recess, destroy thereby advance, thereby concavo-convex little situation can improve the weather resistance of outside plate.

FRP sheet material can obtain by even covering with paint methods such as curing and demolding and then enforcement spray guns.Mould shrinkage, the thermal contraction of the resin during owing to be shaped also can influence surface quality, thereby the mould shrinkage circlet epoxy resins of preferred resin, have sneaked into the low shrink resin of fillers such as talcum, glass granules and lime carbonate.

Forming temperature is preferably high 10 ℃ or more than it than outside plate institute use temperature, for automobile exterior panel, is 90 ℃ or more than it, and more preferably 110 ℃ or more than it is preferred from curring time shortening aspect when 130 ℃ or its are above.

[FRP sheet material]

The thickness of FRP sheet material is different because of purposes, but the situation of the outside plate of the transportation means that automobile etc. move on the ground preferably is in the scope of 0.5～8mm.If below this scope, anti-penetrability may have problem; If more than this scope, then light weight is insufficient.

Aloft the situation of Yun Hang transportation means because speed is faster, thereby is preferably the scope of 1～10mm.

In addition, sandwich structure, ripple struction or also be preferred scheme in the structure that the part of outside plate is provided with framework.

FRP sheet material for Third Way, by using the successive carbon fiber as fortifying fibre, can show the high elastic coefficient and the intensity of one of characteristics as carbon fiber, can realize resistance, rigidity sense, intensity with light weight as the necessary corresponding depression of outside plate.And owing to be continuous fibre, can obtain as the very important characteristic of outside plate is the anti-impact characteristics that runs through.That is, can obtain with the irrealizable lightweight of staple fibre, rigidity and impact characteristics.Certainly, resistance to deformation, ultimate load, addendum modification, energy absorption are also big.

And then continuous fibre has fabric shape, therefore with lamination the situation of the prepreg arranged a direction compare, though be the fortifying fibre of same amount, the anti-impact characteristics that runs through can be higher.Its principle is that fabric is the staggered similar netted structure of fiber, thereby can catch sudden thing.

And, fabric with lamination equate and the situation of the prepreg arranged a direction is compared in the rerum natura of orthogonal 2 directions of one deck (individual layer), just can constitute outside plate with few sheet number, thus more lightweight.For example, the outside plate of lamination if make 2 prepreg quadratures is then because the thermal contraction when solidifying can produce the outer torsional deformation of face that is called as saddle type.The outer distortion of this face is not from external force, can be produced by temperature variation yet.Also can produce when in-plane stress acts on outside plate, thereby the outside plate distortion is lost shape, not preferred from outward appearance aspect, aerodynamic force aspect.

And then, by with light weight and high elastic coefficient, high-intensity carbon fiber as fortifying fibre, can make the outside plate light weight and have high mechanical properties, and, also superior aspect environment resistant.

[covering with paint]

FRP sheet material of the present invention can be implemented on the surface to cover with paint, lacquer, colour wash, etc.Covering with paint will approach (being generally smaller or equal to 150 microns) than gel coat, and light weight.By covering with paint, lacquer, colour wash, etc., not only the selection branch of color but also characteristic is also many.By selected suitable coating, can give characteristic or function that the gloss on surface or concavo-convex, low temperature and hot environment, water tolerance, UV resistant environment etc. only depend on FRP sheet material then can't have, produce practicality first as outside plate.

For example, be divided into the such situation of resin a little less than the UV resistant,, can give UV resistant characteristic as outside plate by implementing the superior covering with paint of UV resistant for the resin portion of FRP sheet material.Certainly, various outward appearances (cosmetic) also are fine, and it also is preferred covering with paint, lacquer, colour wash, etc. from the outward appearance aspect.For outside plate, match colors from needs such as consideration grade and miscellaneous part to safety, can carry out delicate color matching by covering with paint, lacquer, colour wash, etc.In addition, by covering with paint, lacquer, colour wash, etc., moisture and light can not be directly incident on FRP, thereby can obtain environment resistant superior high durable outside plate.And covering with paint, lacquer, colour wash, etc. also is preferred from the fluid resistance aspect.

In addition, cover with paint, lacquer, colour wash, etc. thickness and be preferably 20～200 μ m.If surpass 200 μ m, then film and peel off easily, also not preferred aspect mechanical characteristics and outward appearance.If less than 20 μ m, then light such as sunlight can direct incident, causes deterioration, and be easy to generate the coating spot, and is also not preferred from the aesthetic appearance aspect.Needn't gain in weight by being in this scope, both can forming, also ideal FRP outside plate of weather resistance aspect.40～100 μ m more preferably.

Coating can be selected from following coating, and for example silicon/epoxy is synthetic resin coating and water soluble resin coating such as cold coating, acrylic resin paint, ammonia ester resin paint, Polyester resin lacquer, epoxypaint, fluorine resin coating, cashew resin coating, phthalic resin coating, amino alkyd resin coating, phenolic resin paint, oil paint, Oil varnish, Nitrocellulose pyroxylin(e)finish, comprises the coating of priming paint surfacer, priming paint surfacer putty etc.

Coating roughly is divided into the seasoning of a liquid type, binary liquid shape, mulit liquid type or Air drying coating, baking vanish, ultraviolet curing coating, electron(beam)curing coating etc.And, according to coating method, can be divided into spraying with coating, roller coat with coating, flow coat with coating, brush with coating etc.

In addition, for selecting of coating, preferably select with the good coating of the resin bond of FRP and form.And, because FRP is poorer than its ultraviolet resistance with metallographic phase, thereby the preferred superior coating of weathering resistance.Specifically, be the coating that is called sunlight barrier coating and ultraviolet isolating paint, have in the vehicle of pure acid acrylic acid ammonia ester with carbon black as pigment and cooperate UV light absorber or reduction telomer polyprotonic acid etc. and the coating that obtains, vinylformic acid ammonia ester epoxy organosilicon coating, the fluorine that has added black pigments such as cobalt oxide, cupric oxide, iron oxide black are coating etc.Particularly for the situation of transparent coating, above-mentioned additive is indispensable.

Also have, preferably be dispersed with the electrically conducting coating of conductive filler materials such as carbon black or graphite, metal-powder.Added the coating of the electrical conductor of stannic oxide or weisspiessglanz system, owing to can form transparent conducting coat, therefore, utilizing the situation of aesthetic appearance of carbon fibre fabric or purpose is that it is preferred electrically conducting coating when giving the anti-static effect that can suppress the outside plate that the dust that caused by static and dirt be attached to automobile etc.

In addition, for the outside plate that is starved of the transportation means that arouses attention at night etc., externally to implement the luminous paint (luminescent coating) that JIS K5671 put down in writing also be effective for a slab integral or a part.

Coating method covers with paint, lacquer, colour wash, etc. (electrostatic spray mode and spray gun mode etc.) except spraying (blowing attached) and cover with paint, lacquer, colour wash, etc. (air gun and no air mode etc.), static, electroplate and cover with paint, lacquer, colour wash, etc. (cationic and anionic etc.), powder is covered with paint, lacquer, colour wash, etc. (molten method, mobile impregnating method, the static powder covering with paint method etc. of penetrating), can also be suitable for known special covering with paint method.

Wherein, the FRP sheet material of the manner is because thermotolerance is lower than metal, thus drying temperature smaller or equal to 120 ℃, cover with paint, lacquer, colour wash, etc. superior aspect the coated property as anodic static with FRP, from but preferred.And because carbon fiber is an electroconductibility, thereby the static covering with paint also is the high preferred covering with paint method of coating service efficiency.

In addition, when implementing certain thickness covering with paint, degreasing or the polishing in order to remove releasing agent preferably implemented on the surface of FRP sheet material.By using non-silicon is that material can not need or reduce degreasing or polishing operation as releasing agent.The temperature of covering with paint, lacquer, colour wash, etc. and the heat resisting temperature of outside plate are closely related, preferably cover with paint, lacquer, colour wash, etc. drying near heat resisting temperature.The automobile situation of outside plate, heat resisting temperature is about 100 ℃, the drying temperature of coating is preferably 60～110 ℃ scope.And be about 3 minutes～60 minutes time of drying.

The color of covering with paint, lacquer, colour wash, etc. is determined by the color matching with miscellaneous part, but for the FRP outside plate of carbon fibre fabric as the manner of reinforcement base material, preferably carries out using the deterioration state of visual observations FRP part, the transparent coating of internal injury state.Owing to be transparent,, also have and make the effect that only the experienced third party of metal outer panel is produced the chance of use FRP outside plate so can hold the state of FRP exactly.Certainly, transparent coating also has the aesthetic appearance of utilizing woven fabric structure and the effect that improves commodity value.In addition, transparent coating can be all of outside plate, also can be a part.

In addition, the representative substances of Clear paint is that silicon/epoxy is coating, acrylic acid series coating, but also can be mixture, the alloy system of ammonia ester system or these coating, can also be colored transparent.

For carbon fibre fabric, the fabric of the structure that the ratio of mass area ratio and thickness is big suits.Covering with paint employing spray gun etc. can form the covering with paint method of filming of uniform and thin.The too thin or too thick tendency that the mapping boldness exist to be reduced if film, thereby to be preferably formed be suitable thickness.

[purposes of FRP sheet material]

The FRP sheet material of the manner can be used as the inside and outside plate of transportation means such as cart, automobile, hot-short, high-speed vessel, bicycle, bike, flyer.

Specifically, be following purposes: motorbike frame, nose cone, cart panels such as splash pan, car door, hood, tail gate, side mudguard, side panel, splash pan, trunk lid, top cover, the side mirror lid, spoiler, scatterer, car panel such as luggage carrier, engine cylinder cover, hood, trolley part purposes such as chassis, vehicle headstock ahead, top cover, side panel, car door, the chassis lid, vehicle outside plate purposes such as side skirt, the goods canopy, the indoor utensil of vehicles such as seat, aerofoil profile inner panel in the aerofoil profile truck, outside plate, top cover, base plate etc., be installed in the gas components purposes of air disturbance device on automobile or the bicycle and side skirt etc., window frame, the goods canopy, the seat, base plate, wing, water screw, flyer purposes such as body, notebook computer, the framework purposes of mobile telephone etc., the X ray box, medical usages such as top board, the dynamic planar loudspeakers panel, audio and video products purposes such as diffuser, golf balls, floral disc, ski, aquaplane, backplate (rugby, baseball, hockey, skiing etc.) sports goods purposes, the plate clockwork spring, air vane, elevator (frame panel, the door) etc. general industry purposes.In addition, said sheet material is not only flat board among the present invention, also comprises the sheet material with curvature certainly.

Cubic formula

Below explain at cubic formula of the present invention, and then the explanation of sentence and preferably creating conditions etc. is described.

Provide in the cubic formula and used compression forming method can make the superior method of the superior formed product of fiber-reinforced composite material of high strength and aesthetic appearance at short notice.

(continuous reinforcing fiber is in fact soaked into compositions of thermosetting resin and the shaped material that forms)

The fortifying fibre that can use in the manner can use at the fortifying fibre described in the Third Way, and its preferred example equally also is preferred in the manner.

The compositions of thermosetting resin that uses in cubic formula gets final product so long as can be used as the known thermosetting resin of the matrix resin of FRP, can use any one of Resins, epoxy, unsaturated ethylene ester resin, bimaleimide resin etc. aptly.Wherein, if consider the mechanical properties of molding, the mechanical characteristics after the curing high and with the superior Resins, epoxy of the binding property of fortifying fibre can the use of optimum ground.

In the manner, also can replace above-mentioned shaped material, use the material that continuous reinforcing fiber is in fact soaked into thermosetting resin and at least one side surface and have that material that fortifying fibre to the staple fibre shape soaks into thermosetting resin overlaps and the shaped material that forms.Soak into the material of thermosetting resin as fortifying fibre, can suit to use a material that becomes the fortifying fibre of 12～50mm to soak into to the severing that is commonly called SMC with above-mentioned thermosetting resin to the staple fibre shape.

The fortifying fibre of staple fibre shape is soaked into material behind the thermosetting resin, because the orientation of fortifying fibre is random, thereby compare with the shaped material that only forms by continuous reinforcing fiber in fact, have the advantage that FRP is easy to carry over the complicated shape with rib structure or bulge-structure, but have the shortcoming of mechanical properties difference.Therefore, compression molding can obtain having concurrently FRP both strong points, that mechanical properties is superior, that have complicated shapes such as rib structure or bulge-structure by overlapping both.

At this, soak into thermosetting resin in the material behind the thermosetting resin as fortifying fibre to the staple fibre shape, can use and the same resin of material that continuous reinforcing fiber is in fact soaked into behind the thermosetting resin, also can use different resins.

(mould)

In the manufacture method of the FRP of cubic formula, the preferred use has the mould that can keep the structure of mould inside when close die airtightly.In the manner, mould is desired airtightly to be meant the shaped material of putting into abundant amount in mould and to be full of mould that the thermosetting resin that constitutes shaped material when pressurization in fact can not spill from mould yet.As the structure that keeps mould inside airtightly, the part that upper die and lower die in the time of can making close die (formpiston and former) contact adopts common edge structure (with reference to Fig. 2) or rubber sealing structure.So long as can keep the structure of mould inside airtightly, also can adopt known any structure.

In addition, the air that remains in mould inside during close die becomes the reason in the space of the pin hole on FRP surface and FRP inside sometimes, but, if use mould as mould with deaerating mechanism, when the whole inside of mould is full of with shaped material, by using deaerating mechanism to outgas, then can remove the air that remains in mould inside effectively.

As deaerating mechanism, can hole to be opened/closed (with reference to Fig. 3) be set at mould inside, open to the mould outside, pump perhaps further is set, reduce pressure.The degassing is by closing when pressurizeing and carry out in the moment perforate that is full of the whole inside of mould with shaped material.

And then the shaping of FRP in order easily to take out FRP, also can be installed the mechanism that ejector pin and air valve (with reference to Fig. 3) etc. make the FRP demoulding after finishing on mould.Thus, do not wait mold cools down just can easily take out FRP, thereby be suitable for mass production.In addition, the mechanism that carries out the demoulding can be ejector pin, air valve or mechanism in addition, also can be known in the past any mechanism.

(manufacture method of FRP)

The method that obtains FRP at using above-mentioned shaped material and mould in conjunction with the accompanying drawings.

Figure 1A is that expression has been placed the figure of the state of shaped material at mould inside before the close die.In addition, 1 shown in a plurality of figure of the manner represent former, 2 expression formpistons, 3 expression common edge structures, 4 expressions hole to be opened/closed, the 5 expression tips (up and down) by air, 6 expression gaskets, the air when A represents perforate flows into, and the air when B represents closed pore flows into.At first, the mould temperature adjustment to the solidification value of the thermosetting resin of shaped material or after more than it, is put into shaped material at mould inside.

Subsequently, form by close die press molding material.Figure 1B is the figure of the state of expression close die.As shown in the drawing, thermosetting resin flows out to mould outside hardly, and shaped material is pressurized and be full of the whole inside of mould.

As previously described, compression molding form by continuous reinforcing fiber prepreg the time coil bending that produces mainly be because the surplus of matrix resin flows.Therefore, in the manner, find, in order to suppress resin flow, (monoplanar surface of FRP is long-pending) the approaching long-pending shaped material of monoplanar surface that is to use the monoplanar surface of the inside when being formed with long-pending with close die, can obtain good effect, specifically, can make continuous reinforcing fiber is in fact soaked into thermosetting resin and the long-pending S of monoplanar surface of the shaped material that forms ₁The monoplanar surface of the mould inside during with close die is amassed S ₂Ratio S ₁/ S ₂Become 0.8～1.If S ₁/ S ₂Less than 0.8 then in the resin flows fierceness of mould inside, is easy to generate coil bending.On the other hand, S ₁/ S ₂Surpass at 1 o'clock,, then can cause the shaped material deficiency in closed mold obstacle or the molding if the circumference of shaped material exposes from mould; If shaped material is folding, then can produce the mixed and disorderly of fibre orientation.At this, so-called monoplanar surface is long-pending to be the surface-area that has one of thickness 2 equal in fact faces at interval basically that constitutes molding.

In addition, particularly obtain the situation of high-quality FRP, volume and height for shaped material also can use near molding (shape of the mould inside during close die) person.Put into the volume of shaped material of mould inside and the volume that thickness is preferably molding respectively 100～120% and thickness 100～150%.

If put into mould inside shaped material the not enough molding of volume volume 100%, then can not apply sufficient pressure to shaped material.On the other hand, if surpass 120%, then shaped material can flow out before obtaining the resistance to air loss of mould, thereby and not preferred.

The thickness of shaped material then is difficult to whole faces of shaped material are pressurizeed equably with respect to the thickness less than 100% of FRP, above 150% o'clock, thereby and not preferred.At this, the thickness of so-called shaped material and the thickness of FRP are mean thicknesss separately.

In the manner, need be with the temperature adjustment in advance of above-mentioned mould to the solidification value of thermosetting resin or more than it.At this moment, thermoregulated temperature is so long as by the solidification value of forming decision of thermosetting resin or more than it, can select better temperature according to the molding condition beyond composition and the temperature.

In the manufacture method of the FRP of the manner, the pressure when carrying out compression molding can be known pressure when carrying out compression molding, is not particularly limited.Can be according to the decisions aptly such as shape of FRP.

Embodiment

Followingly specifically describe 4 kinds of modes of the present invention according to embodiment.

The embodiment of first mode

In present embodiment and comparative example, used following with being called for short the material of representing.Median size is the value of measuring with the laser diffraction and scattering method.In addition, the manner is not limited to following embodiment.

＜Resins, epoxy 〉

EP828: japan epoxy resin (strain) system エ ピ コ-ト 828 (registered trademark, bisphenol A type epoxy resin, 120p/25 ℃)

EP807: japan epoxy resin (strain) system エ ピ コ-ト 807 (registered trademark, bisphenol f type epoxy resin, 30p/25 ℃)

EP604: japan epoxy resin (strain) system エ ピ コ-ト 604 (registered trademark, glycidyl amine type epoxy resins)

N740: big Japanese ink chemical industry (strain) system EPICLON N-740 (phenolic resin varnish type epoxy resin, semi-solid state)

YCDN701: Dongdu changes into (strain) system Off エ ノ ト-ト YCDN701 (cresols varnish type Resins, epoxy)

Off レ Star プ 50: eastern Li Juliuxiangjiaoshe system Resins, epoxy, registered trademark

EXA1514: the EPICLON EXA1514 of Dainippon Ink. ﹠ Chemicals Inc bisphenol-s epoxy resin

＜have an amine compound of at least one sulphur atom at intramolecularly 〉

DDS: Wakayama refine (strain) system セ イ カ キ ユ ア-S (diaminodiphenylsulfone(DDS), registered trademark, sulphur atom content are 12.9 quality %)

BAPS: Wakayama refine (strain) system BAPS (4,4 '-diamino-diphenyl sulfide, sulphur atom content are 7.4 quality %)

BAPS-M: Wakayama refine (strain) system BAPS-M (two (4-(3-amino-benzene oxygen) benzene) sulfone, sulphur atom content are 7.4 quality %)

ASD: Wakayama refine (strain) system ASD (4,4 '-diamino-diphenyl sulfide, sulphur atom content are 14.8 quality %)

TSN: Wakayama refine (strain) system TSN (o-tolidine sulfone, sulphur atom content are 11.7 quality %)

＜urea compounds 〉

PDMU: phenyl dimethyl urea (median size is 50 μ m)

DCMU:3,4-dichlorophenyl-N, N-dimethyl urea (median size is 50 μ m)

＜Dyhard RU 100 〉

DICY7: Dyhard RU 100 (median size is 7 μ m)

DICY15: Dyhard RU 100 (median size is 15 μ m)

DICY1400: Dyhard RU 100 (median size is 20 μ m)

＜additive 〉

PVF: チ Star ソ (strain) makes PVC ニ レ Star Network E (polyvinylformal)

YP50: Dongdu changes into (strain) system Off エ ノ ト-ト YP50

Aerosil: Japanese ア エ ロ ジ Le (strain) system, ア エ ロ ジ Le 300

(evaluation method)

The resin combination that uses the manner is with method manufacturing prepreg described later, but measures its gel time between the usage period, mechanical properties.Measuring method is as follows.

(1) gel time

Cut out the square sample of length of side 2mm from prepreg, clamp with 2 sheet glass cover plates.Place it on the hot-plate that is controlled to 130 ℃ ± 0.5 ℃.Measure time of origin as gel time placing in an instant behind the sample.Push prepreg repeatedly with tweezers etc. every now and then, confirm the state of composition epoxy resin, measure time that gelation finishes fully and with it as gel time.The immobilising state of composition epoxy resin when said here complete gelation is meant and pushes with tweezers etc.

(2) but between the usage period

Prepreg is put into 30 ± 1 ℃ thermostatic drier, observe every day, the longest be the binding property of the prepreg after 21 days, binding property is lost (prepreg is not bonded to each other) but fate as between the usage period.

(3) mechanical properties

By the vacuum bag shaping prepreg is formed, make the flat fibre reinforced composites of vertical 200mm * horizontal 200mm * thick 150mm.Measure 0 ° of flexural strength and 90 ° of flexural strengths of this flat board according to ASTM D 790.

(content of sulphur atom)

When the A composition does not have sulphur atom, the summation of the mass parts of the A composition, C composition, D composition and the additive that add is counted X, the mass parts of the B-1 composition that uses in the manufacturing of composition epoxy resin is counted Y and the content of the sulphur atom in the B-1 composition that uses in the manufacturing of composition epoxy resin is counted p (quality %), and then the content S of sulphur atom can be obtained by following formula.

S (quality %)=pY/ (X+Y)

When the A composition has sulphur atom, directly measure from composition epoxy resin with following atomic absorption spectrometry.That is, make after the composition epoxy resin, in aqueous nitric acid, decompose this composition epoxy resin of 50mg, utilize ion exchanged water to dilute this solution again to 50ml, with this aqueous solution as working sample.

Use high frequency plasma apparatus for analyzing luminosity (Japanese ジ ヤ-レ Le ア Star シ ユ society system, ICAP-575MK-II) to carry out mensuration (condition determination: plasma gas is 180.7nm as 16L/min, carrier gas as 0.48L/min, mensuration wavelength as 0.8L/min, heat-eliminating medium gas) for this working sample by the sulphur atom concentration of atomic absorption spectrometry.Use the typical curve make in advance to obtain the concentration of the sulphur atom in the aqueous solution, and then calculate sulphur atom content (quality %) this composition epoxy resin from the concentration of this sulphur atom.

Embodiment 1～10

Be mixed to evenly the modulating epoxy resin composition with the ratio of components shown in the table 1.Is 33.7g/m with simple type roller coat device with the resin mass area ratio ²This composition epoxy resin is coated on the release paper equably, forms resin layer.Attaching to this resin layer with the fiber mass area ratio is 125g/m ²Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, modulus in tension: 240GPa) and after the two sides of the board that forms, with roller with 100 ℃, line pressure 2kg/cm heats and pressurize, composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m ²The prepreg of (resin content is 35 quality %).

But the prepreg that the composition epoxy resin by embodiment 1～10 is obtained at 130 ℃ gel time and estimate between the usage period, consequently, gel time is all smaller or equal to 200 seconds, but and between the usage period, also can keep binding property during through 21 days, but thereby can confirm more than or equal between 21 days usage period.

Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of flexural strength is all above 160kg/mm ², 90 ° of flexural strengths are all above 10kg/mm ², demonstrate good rerum natura.

Embodiment 11～20

Except be mixed to evenly with the ratio of components shown in the table 2, complete and embodiment 1 similarly makes prepreg, and has implemented evaluation.

The prepreg that is obtained by the composition epoxy resin of embodiment 11～20 also is, gel time is all smaller or equal to 200 seconds, but and can confirm more than or equal between 21 days usage period.

Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of flexural strength is all above 160kg/mm ², 90 ° of flexural strengths are all above 10kg/mm ², demonstrate good rerum natura.

Embodiment 21

In the composition shown in the embodiment 21 of table 3, at the Resins, epoxy of mixed at room temperature B composition and amine component (DDS) afterwards, heat at 150 ℃ that to make part reaction, the viscosity that is modulated into 90 ℃ be 30～90 pools (B-2 composition).This reactant and A composition and C, D composition are mixed to evenly the modulating epoxy resin composition with the ratio of components shown in the embodiment 21 of table 3.Is 33.7g/m with simple type roller coat device with the resin mass area ratio ²This composition epoxy resin is coated on the release paper equably, forms resin layer.Attaching to this resin layer with the fiber mass area ratio is 125g/m ²Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, modulus in tension: 240GPa) and after the two sides of the board that forms, with roller with 100 ℃, line pressure 2kg/cm heats and pressurize, composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m ²The prepreg of (resin content is 35 quality %).

But the prepreg that the composition epoxy resin by embodiment 21 is obtained at 130 ℃ gel time and estimate between the usage period, consequently, gel time is all smaller or equal to 200 seconds, but and between the usage period, also can keep binding property during through 21 days, but thereby can confirm more than or equal between 21 days usage period.

Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of flexural strength is all above 160kg/mm ², 90 ° of flexural strengths are all above 10kg/mm ², demonstrate good rerum natura.

Embodiment 22～31

With the ratio of components shown in the table 3 afterwards, heat at 150 ℃ and to make part reaction, and to be modulated into 90 ℃ viscosity be 30～90 pools at the Resins, epoxy of mixed at room temperature A composition and amine component (DDS).Except being mixed to evenly with the ratio of components shown in the table 3 this reactant and B composition and C composition, fully and embodiment 21 similarly make prepreg, and implemented evaluation.

The prepreg that is obtained by the composition epoxy resin of embodiment 22～31 also is, gel time is all smaller or equal to 200 seconds, but and also can confirm more than or equal between 21 days usage period.

Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of flexural strength is all above 160kg/mm ², 90 ° of flexural strengths are all above 10kg/mm ², demonstrate good rerum natura.

Embodiment 32～45

, after the Resins, epoxy and amine component of mixed at room temperature A composition, heat at 150 ℃ and to make a part of reaction with the ratio of components shown in the table 4, and to be modulated into 90 ℃ viscosity be 30～90 pools.Except being mixed to evenly with the ratio of components shown in the table 4 this reactant and B composition and C composition, fully and embodiment 21 similarly make prepreg, and implemented evaluation.

The prepreg that is obtained by the composition epoxy resin of embodiment 32～45 also is, gel time is all smaller or equal to 200 seconds, but and also can confirm more than or equal between 21 days usage period.

Comparative example 1～8

Except be mixed to evenly with the ratio of components shown in the table 5, complete and embodiment 1 similarly makes prepreg, and has implemented evaluation.

Consequently, except comparative example 2,4,6, gel time does not perhaps solidify with interior also the end in a few hours all above 200 seconds.Comparative example 2,4,6 has shown gel time smaller or equal to 200 seconds rapidly-curable, but but short between the usage period, for smaller or equal to 5 days.

Comparative example 9～10

Except be mixed to evenly with the ratio of components shown in the table 3, complete and embodiment 21 similarly makes prepreg, and has implemented evaluation.

Consequently, for the comparative example 9 and 10 that does not contain Dyhard RU 100, although cooperated the amount identical with embodiment 21 and embodiment 24 as the total amount of solidifying agent, but compare with the flat plate composite of in each embodiment, making, only can obtain the flat plate composite of 0 ° of flexural strength low about 10%.And then, be prepreg below 5 days but in comparative example 10, become weak point between the usage period.

Describe in detail as above, the composition epoxy resin of the manner just can solidify at short notice in lower temperature.Thereby, even but the prepreg that can obtain using this composition epoxy resin to obtain also have between the sufficient usage period in room temperature preservation, and show this effect of superior mechanical properties by the matrix material that this prepreg obtains.And then proved, can in the shaping of fibre reinforced composites, shorten process period by using this prepreg, thereby can low-costly make.

Table 1

Composition		The resin name	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 44	Embodiment 45
															A composition (mass parts)	Resins, epoxy	EP828	86	84	82	78	68							33
EP807						86	68	34	70	61
													N740													43
フレツプ50											30
													EXA1514														40
B composition (mass parts)	Amine compound with sulphur atom	DDS	2	4	6	10	20	2	20	54	20	20																10	10
													BAPS
		BAPS-M
													ASD
		TSN
													C composition (mass parts)	Urea compounds	PDMU	5	5	5	5	5
DCMU						5	5	5	3	12	10	10
															D composition (mass parts)	Dyhard RU 100	DICY1400									7	7
DICY15						7	7	7
													DICY7	7			7	7	7	7						7	7
Additive (mass parts)		ビニレツクE
													YP50
		アエロジル300
													Sulphur atom content (%)			0.26	0.52	0.77	1.29	2.58	0.26	2.58	6.98	2.58	2.58			6.5	6.1
Gel time (S)			190	170	160	155	150	190	155	130	170	160														190	190
													Serviceable time		My god	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21			＞21	＞21
Mechanical properties		0 ° of pliability test (Kg/mm)	168	173	175	170	172	171	164	163	170	175														167	170
													90 ° of pliability tests (Kg/mm)	12.6	12.4	12.4	12.3	13.9	13.1	13.7	13.5	14.5	14.5	13.5	14.0

Table 2

Composition		The resin name	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17	Embodiment 18	Embodiment 19	Embodiment 20
													The A composition	Resins, epoxy	EP828					77	77	77	77	77
EP807	58
											N740				70
YCDN701			70
											EP604						70						54
The B composition	Amine compound with sulphur atom	DDS	20				10																		30
											BAPS		20	20	20		10
		BAPS-M							10
											ASD								10
		TSN																				10
											The C composition	Urea compounds	PDMU		5	5	5								5
DCMU	15				5	5	5	5	5
													The D composition	Dyhard RU 100	DICY1400	7
DICY15		5	5	5	5	5
											DICY7									5	5	5	5
Additive		ビニレツクE					3	3	3																3
											YP50								3	3
		アエロジル300																					3
											Sulphur atom content (%)			2.58	1.48	1.48	1.48	1.29	1.29	1.29	1.48			1.17	3.87
Gel time (S)			155	180	170	155	165	170	176	175												180	160
											Serviceable time		My god	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21			＞21	＞21
Mechanical properties		0 ° of pliability test (Kg/mm)	168	166	164	164	168	171	165	167												166	172
											90 ° of pliability tests (Kg/mm)	12.4	12.1	12.5	12.4	12.5	12.7	12.5	12.2	12.3	12.9

Table 3

Composition		The resin name	Embodiment 21	Embodiment 22	Embodiment 23	Embodiment 24	Embodiment 25	Embodiment 26	Embodiment 27	Embodiment 28	Embodiment 29	Embodiment 30	Embodiment 31	Comparative example 9	Comparative example 10
																The A composition	Resins, epoxy	EP828	5	5	5	5	5							5
EP807						5	5	5	5	5	5		5
														N740
YCDN701
														EP604
The B-2 composition	Resins, epoxy has the amine compound of sulphur atom	EP828	81	79	77	73	63																							77
														EP807						81	63	29	65	56	53		56
		N740
														YCDN701
		EP604
														DDS	2	4	6	10	20	2	20	54	20	20	20	6	20
		BAPS
														BAPS-M
		ASD
														TSN
		The C composition	Urea compounds	PDMU	5	5	5	5	5																					5
DCMU																		5	5	5	3	12	15		12
				The D composition	Dyhard RU 100	DICY1400																					7	7	7
DICY15																7	7	7
						DICY7	7	7	7	7	7
Additive		ビニレツクE
				YP50
		アエロジル300
				Evaluation result
Sulphur atom content (%)			0.26											0.52	0.77	129	2.58	0.26	2.58	6.98	2.58	2.58	2.58					0.77	2.58
				Gel time (S)			185	165	150	150	140	180	145											100	145	150	145			230	225
Serviceable time		My god	＞21											＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21	＞21					＞21	4
				Mechanical properties		0 ° of pliability test (Kg/mm)	175	172	172	169	168	171	166											168	174	168	169			150	155
90 ° of pliability tests (Kg/mm)	13.1	12.9	12.3											12.5	12.7	12.6	12.4	12.4	12.9	13.2	12.5	10.0	10.0

Table 4

Composition		The resin name	Embodiment 32	Embodiment 33	Embodiment 34	Embodiment 35	Embodiment 36	Embodiment 37	Embodiment 38	Embodiment 39	Embodiment 40	Embodiment 41	Embodiment 42	Embodiment 43
															The A composition	Resins, epoxy	EP828				5	5	5	5	5		5	5	5
EP807
													N740	5
YCDN701		5
													EP604					5						5
The B-2 composition	Resins, epoxy has the amine compound of sulphur atom	EP828				72	72	72	72	72		75																68	63
													EP807	65
		N740		65
													YCDN701			65
		EP604									49
													DDS				10					30	10	10	10
		BAPS	20	20	20		10
													BAPS-M						10
		ASD							10
													TSN								10
		The C composition	Urea compounds	PDMU	5	5	5																			5	3	10	15
DCMU															5	5	5	5	5
				The D composition	Dyhard RU 100	DICY1400
DICY15	5	5	5										5	5
						DICY7						5										5	5	5	7	7	7
Additive		ビニレツクE													3	3	3			3
				YP50							3	3
		アエロジル300																		3
				Sulphur atom content (%)			2.58	2.58	2.58	1.29	1.29	1.29										1.29	1.29	2.58	1.29			1.29	1.29
Gel time (S)			170										160	145	160	160	170	175	175	150	180					160	140
				Serviceable time		My god	＞21	＞21	＞21	＞21	＞21	＞21										＞21	＞21	＞21	＞21			＞21	＞21
Mechanical properties		0 ° of pliability test (Kg/mm)	164										172	175	170	172	164	169	168	177	172					175	173
				90 ° of pliability tests (Kg/mm)	12.2	12.4	12.3	11.9	12.6	12.4	12.3	12.7										12.0	13.1	12.8	12.9

Table 5

Composition		The resin name	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7	Comparative example 8
											The A composition	Resins, epoxy	EP828	87	33					75	70
EP807			72.1	57	72.1	57
									The B-1 composition	Amine compound with sulphur atom			DDS	1	55	20	20			20	20
BAPS
											BAPS-M
ASD					20	20
											TSN
The C composition	Urea compounds	PDMU	5	5	0.9	16
									DCMU					0.9	16	5	10
									The D composition	Dyhard RU 100	DICY1400	7	7	7	7
DICY15					7	7
											DICY7
Sulphur atom content (%)			0.13	7.10	2.58	2.58	2.96	2.96												2.58	2.58
									Gel time (S)			250	170	-	160	-	160	250	250
Serviceable time		My god	＞21	5	＞21	4	＞21	4												＞21	＞21
									Mechanical properties		0 ° of pliability test (Kg/mm)	155	173	168	159	169	161	164	163
90 ° of pliability tests (Kg/mm)	12.0	12.3	12.4	12.3	12.2	13.1	13.7	13.5

"-" representative ring epoxy resins on gel time hurdle does not have gelation.

The embodiment of second mode

Below, explain second mode of the present invention based on embodiment.In addition, the manner is not limited to following embodiment.

As the starting material of compositions of thermosetting resin, prepare following Resins, epoxy and solidifying agent.

＜Resins, epoxy 〉

EP828：

The system liquid bisphenol A of japan epoxy resin society type Resins, epoxy, エ ピ コ-ト 828 (registered trademark)

EP1009：

The solid-state bisphenol A type epoxy resin of japan epoxy resin society system, エ ピ コ-ト 1009 (registered trademark)

AER4152：

Society of Asahi Chemical Industry system Resins, epoxy, ア ラ Le ダ イ ト AER4152 (registered trademark)

N740：

Big Japanese ink chemical industry society system phenolic resin varnish type epoxy resin, エ ピ Network ロ Application N-740 (registered trademark)

＜solidifying agent 〉

HX3722：

Society of Asahi Chemical Industry system microcapsule-type potentiality solidifying agent, ノ バ キ ユ ア HX3722 (registered trademark)

FXE1000：

Fuji changes into society's system used for epoxy resin potentiality solidifying agent, Off ジ キ ユ ア FXE1000

PDMU：

PTI Japan society system phenyl dimethyl urea, オ ミ キ ユ ア 94 (registered trademarks)

DCMU：

Protect the chemical society of native ケ paddy system 3,4-dichlorophenyl-N, N-Dimethylurea, DCMU99

Dicy：

Japan epoxy resin society system Dyhard RU 100, Dicy7

2P4MZ：

Four countries change into the system 2-of society phenyl-4-methylimidazole

＜viscosimetric analysis 〉

Device: Rheometrics corporate system RDS-200

Mode determination: parallel plate (25mm φ, interval 0.5mm)

Frequency: 1Hz

Temperature is set: from 50 ℃ with 10 ℃ of/minute intensification, reach 120 ℃ after mensuration isothermal viscosity

Determination data: surpass 10 by viscosity 50 ℃ viscosity, after reaching 120 ℃ ²The time of Pasec.In the present embodiment, can confirm that the viscosity of whole compositions of thermosetting resin when reaching 120 ℃ is smaller or equal to 10 ¹Pasec.

Tackify after＜30 ℃ * 3 weeks 〉

Sample at once after having modulated compositions of thermosetting resin, be determined at 50 ℃ viscosities il by above-mentioned viscometry ₀, same compositions of thermosetting resin was placed for 3 weeks in 30 ℃ drying machine, through after being subjected to thermal process, similarly implement viscosimetric analysis, be determined at 50 ℃ viscosities il ₁Tackify passes through η ₁/ η ₀Obtain.

The modulation of＜prepreg 〉

Compositions of thermosetting resin is warming up to 50 ℃ to reduce viscosity, is coated on thinly again and modulates the heat fusing film on the release paper, the system carbon fibre fabric TR3110 of Li Yang society of Mitsubishi is soaked into this heat fusing film and obtains prepreg.Resin content is adjusted into 30 quality %.

＜be shaped

11 layers of prepreg of lamination in the same direction use to have the metal die of common edge with the compacting pressure of 2MPa, form with thermocompressor.The thickness of forming board is roughly 2mm.

＜mechanical properties is measured 〉

Use Instron corporate system universal testing machine, pliability test is implemented interlayer shear test (ILSS) according to ASTMD2344 according to ASTM D790.

Embodiment 46～50

With the modulation of the composition shown in the table 6 compositions of thermosetting resin, carry out 50 ℃ viscosimetric analysis, 50 ℃ viscosimetric analysis after 30 ℃ * 3 weeks.After reaching 120 ℃, mensuration surpasses 10 by viscosity ²The time of Pasec.Make the sense of prepreg armrest and implement the evaluation of operability.Suitable and easy handling is designated as " zero ", unworkable be designated as " * " viscosity, drape.And, the prepreg after the modulation was placed for 3 weeks at 30 ℃, similarly estimate at operability subsequently.And then by above-mentioned method shaping prepreg.Shaping is to implement under 3 conditions of 120 ℃ * 15 minutes, 120 ℃ * 10 minutes, 140 ℃ * 4 minutes, measures mechanical properties respectively.Conclusion the results are shown in the table 6.Compositions of thermosetting resin in an embodiment, soon operability, the modulation back of prepreg is well 30 ℃ of operability through the prepreg after 3 weeks after the modulation.Appearance after the shaping is also beautiful, and mechanical properties is also good.

Comparative example 13 (at the low example of 50 ℃ viscosity)

With the modulation of the composition shown in the table 7 compositions of thermosetting resin.Because 50 ℃ viscosity less than 5 * 10 ¹Pasec, thereby soon its viscosity of prepreg is very strong, slimy after the modulation, is difficult to operation.

Comparative example 14 (at the high example of 50 ℃ viscosity)

With the modulation of the composition shown in the table 7 compositions of thermosetting resin.Because 50 ℃ viscosity surpasses 1 * 10 ⁴Pasec, thereby compositions of thermosetting resin is stone, can not filming.

Comparative example 15 (tackify of the viscosity after 30 ℃ * 3 weeks surpasses 2 times example)

With the modulation of the composition shown in the table 7 compositions of thermosetting resin.This compositions of thermosetting resin after 30 ℃ * 3 weeks is stone, can not measure viscosity.In addition, soon the operability of prepreg is good after the modulation, but places the back hardening of 3 weeks in room temperature, becomes the state of end-of-life.

Comparative example 16 (120 ℃ 10 ⁶Surpass Pasec time of arrival 1000 seconds example)

With the modulation of the composition shown in the table 7 compositions of thermosetting resin.120 ℃ 10 ⁶Pasec reaches 1300 seconds time of arrival, compares with embodiment, can know that obviously solidified nature is poor.In addition, pliability test is because not fracture, thereby is decided to be " can not measure ".

As mentioned above, the compositions of thermosetting resin of the manner can provide the compositions of thermosetting resin of the matrix resin that is suitable for prepreg, described prepreg is in the operability of room temperature and good in the long lifetime property of room temperature, and when keeping the good rerum natura after the shaping, can carry out the desired high-rate forming of industry purposes.

As mentioned above, the prepreg of the manner is in the operability of room temperature and superior in the long lifetime property of room temperature, and when keeping good rerum natura after the shaping, can carry out the desired high-rate forming of industry purposes.

Can prove by above, the compositions of thermosetting resin of the manner, prepreg, and the manufacture method of FRP all be suitable for very much high-rate forming, go a long way greatly and reduce shaping process cost as the greatest drawback of FRP.

Table 6

			Embodiment 46	Embodiment 47	Embodiment 48	Embodiment 49	Embodiment 50
								Form	EP828	Part	40	40	60	60	60
EP1009	Part	20	20	20	20	20
							AER4152		Part			20	20	20
N740	Part	40	40
							FXE1000		Part	5
HX3722	Part				5	10
							Dicy		Part	5	5	5	5	5
DCMU	Part		15
							PDMU		Part	5		10	5	5
Viscosity at 50 ℃		Pa·sec	350	380	280	260									230
							Soon the operability of prepreg after the modulation		○/×	○	○	○	○	○
Tackify after 30 ℃ * 3 weeks		Doubly	1.5	1.7	1.4	1.4									1.5
							Modulate the operability of the prepreg after 3 weeks		○/×	○	○	○	○	○
120 ℃ 10 6Pasec time of arrival		Second	530	950	900	780									520
							The flexural strength that was shaped in 120 ℃ * 15 minutes		MPa	1200	1100	1100	1200	1200
Same ILSS		MPa	74	72	73	73									73
							The flexural strength that was shaped in 120 ℃ * 10 minutes		MPa	1100	770	820	950	1200
Same ILSS		MPa	74	65	68	70									74
							The flexural strength that was shaped in 140 ℃ * 5 minutes		MPa	1200	1200	1200	1200	1200
Same ILSS		MPa	75	73	74	72									74

Table 7

			Comparative example 13	Comparative example 14	Comparative example 15	Comparative example 16
							Form	EP828	Part	50	30	40	60
EP1009	Part	10	40	20	20
						AER4152		Part				20
N740	Part	40	30	40
						FXE1000		Part	5	5
Dicy	Part	5	5	5
						PDMU		Part	5	5		7
2P4MZ	Part			5
						Viscosity at 50 ℃		Pa·sec	45	15000	340	270
Soon the operability of prepreg after the modulation		○/×	×		○								○
						Tackify after 30 ℃ * 3 weeks		Doubly	1.3		∞	1.4
Modulate the operability of the prepreg after 3 weeks		○/×	○		×								○
						120 ℃ 10 6Pasec time of arrival		Second	620		960	1300
The flexural strength that was shaped in 120 ℃ * 15 minutes		MPa	1200		1100								Can not measure
						Same ILSS		MPa	73		72	35
The flexural strength that was shaped in 120 ℃ * 10 minutes		MPa	1200		780								Can not measure
						Same ILSS		MPa	72		66	22
The flexural strength that was shaped in 140 ℃ * 5 minutes		MPa	1100		1200								Can not measure
						Same ILSS		MPa	74		73	42

The embodiment of Third Way

Specifically describe Third Way of the present invention by the following examples.In addition, the manner is not limited to following embodiment.

[based on the embodiment of resin combination (1)]

Embodiment 1～20 shown in first mode satisfies desired condition in the manner.The superior result that embodiment 1～20 demonstrates has proved thus that for as described at the embodiment of first mode composition epoxy resin and prepreg that the manner provides have superior characteristic.In addition, the condition that requires in 1～8 discontented unabridged version mode of the comparative example shown in first mode.Proved that thus comparative example 1～8 all can not demonstrate the superior characteristic as embodiment 1～20.

Embodiment 51

Is 26.8g/m with simple type roller coat device with the resin mass area ratio ²The composition epoxy resin that obtains among the embodiment 3 with first mode is coated on the release paper equably, forms resin layer.Being bonded in this resin layer with the fiber mass area ratio is 125g/m ²Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, modulus in tension: 240GPa) and after the two sides of the board that forms, with roller with 100 ℃, line pressure 2kg/cm heats and pressurize, composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m ²The prepreg of (resin content is 30 quality %).

On the other hand, be 164g/m with simple type roller coat device with the resin mass area ratio ²The composition epoxy resin that obtains among the embodiment 3 is coated on the release paper equably, forms resin layer.This resin layer is bonded in the carbon fibre fabric TR3110 of the beautiful sun of Mitsubishi (strain) system, and ((mass area ratio is 200g/m to the fabric that forms with 12.5 pieces/inch plain weave TR30S3L of weaving density (the long filament number is 3000) ²)) on face after, with roller with 100 ℃, line pressure 2kg/cm heats and pressurize, and composition epoxy resin is impregnated in the carbon fiber, making the fiber mass area ratio is 200g/m ²The Fabric prereg of (resin content is 45 quality %).

Prepreg and Fabric prereg are cut into 200 * 200mm, is 0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 ° 16 prepregs of lamination altogether with prepreg with fiber direction, 1 Fabric prereg of (on 0 ° of layer) lamination prepares the prepreg laminate more thereon.

(operable metal die face is 210 * 210mm) to be heated to 130 ℃ to be placed with the metal die of 220 * 220mm of isoprene-isobutylene rubber gasket of wide 10mm, thick 3mm with the L font on will 2 limits in 4 limits.

In the part used of metal die with respectively apart from metal die end or isoprene-isobutylene rubber gasket 5mm and place the prepreg laminate of previous preparation.And closed immediately metal die also applies 15 minutes 10kg/cm ²Pressure, obtain FRP sheet material.

At random cut out the test film of 3 30 * 30mm by FRP sheet material, obtain the volume content (Archimedes's method) of carbon fiber, consequently average out to 60.6 volume %.Using the density 1.25 of matrix resin, the result that the mean density 1.82 of carbon fiber is calculated resin content is 30.9 weight %.

It is concavo-convex that the FRP sheet material that obtains can see sporadicly that the damage owing to the metal die surface produces, and is used in device, the method put down in writing in the detailed description and measures the center line average roughness that does not have concavo-convex part, and its result is 0.27 μ m.

Proof as mentioned above can provide the FRP sheet material of suitable outside plate as transportation means and industrial machine and can be suitable for the prepreg that obtains FRP sheet material by the manner.

The embodiment of cubic formula

Specifically describe cubic formula of the present invention by the following examples.In addition, the manner is not limited to following embodiment.

Embodiment 52

As the structure that keeps mould inside airtightly, the part of upper die and lower die contact adopts common edge structure (with reference to Fig. 2) during close die, will be 900cm except the FRP thickness partly surface-area partly of counterdie ²Mould, upper die and lower die are heated to 140 ℃ simultaneously.

As shaped material, preparation will draw the prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin to cut into 285 * 285mm to a direction, again so that the differently-oriented directivity of fiber is that (thickness is that 2mm, cumulative volume are 162cm for 0 ° and 90 ° of 18 of staggered mode laminations ³, monoplanar surface is long-pending is 812cm ²) and the material that obtains.S ₁/ S ₂Be 812/900=0.9.In addition, the Resins, epoxy that uses in prepreg TR390E125S is for composition epoxy resin following manufacture method manufacturing, that be equivalent to the composition epoxy resin of first mode.

That is, make the mixture (mass ratio is 92: 8) of EP828 and DDS react interpolation 15 mass parts EP828,6 mass parts PDMU, 9 mass parts Dyhard RU 100s in the resin combination that obtains to 100 mass parts at 150 ℃, remix is to uniform composition epoxy resin.

On counterdie, place above-mentioned shaped material, and put down patrix at once and close die applies 10 minutes 9.8 * 10 ²After the pressure of KPa, open mould, the temperature of mould is remained on 140 ℃, take out molding (thickness is that 1.6mm, volume are 144cm by being installed in ejector pin on the mould ³).Its surface of this molding, the back side and cross section all do not have pin hole and space, and outward appearance is superior.

Embodiment 53

As shaped material, use shaped material that to use among the embodiment 1 and the Resins, epoxy SMC Lytex4149 (QUANTUM COMPOSITES society system) that contains carbon fiber (to be 812cm except the single side surface of thickness part is long-pending ²) (total thickness is that 4mm, cumulative volume are 325cm for shaped material after the attaching ³).S ₁/ S ₂Be 0.9.

On counterdie, place above-mentioned shaped material, and put down patrix at once and close die applies 10 minutes 3.0 * 10 ³After the pressure of kPa, open mould, the temperature of mould is remained on 140 ℃, take out molding (thickness 3.2mm, volume 288cm by the ejector pin that is installed on the mould ³).This molding obtains other goods of level that the surface does not have outward appearance transitivity aspect problem yet.

Proof as mentioned above, the manufacture method of the FRP by using the manner is used and is suitable for mass-produced compression forming method, can obtain high strength and aesthetic appearance FRP superior, that formed by continuous reinforcing fiber in fact.

Comparative example 17

Except use as shaped material will to a direction draw prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin cut into 250 * 250mm, again so that the alignment direction of fiber is that (thickness is 162cm as 2.6mm, cumulative volume for 0 ° and 90 ° of 24 of staggered mode laminations ³, monoplanar surface is long-pending is 625cm ²) and beyond the material that obtains and embodiment 1 the same terms form.S ₁/ S ₂Be 625/900=0.7.

Molding is because the mixed and disorderly severity, particularly peripheral part of the fibre orientation that the resin flow in being shaped causes significantly mixed and disorderly.

Comparative example 18

Except using and to draw the prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin to cut into 320 * 320mm to a direction, again so that the differently-oriented directivity of fiber is that (thickness is that 1.6mm, cumulative volume are 162cm for 0 ° and 90 ° of 14 of staggered mode laminations as shaped material ³, monoplanar surface is long-pending is 1024cm ²) and beyond the material that obtains and embodiment 1 the same terms form.S ₁/ S ₂Be 1024/900=1.1.

Owing to constitute the fortifying fibre of shaped material and expose from mould, thereby fiber is drawn out in the shaping, and produces the mixed and disorderly of fibre orientation.Therefore, the molding bad order that obtains also can not get the goods of surface smoothing.

The possibility of utilizing on the industry

By the present invention, can easily provide and give quantitative target, can solidify at short notice in lower temperature, mechanical properties is superior and the FRP of the superior prepreg that at room temperature can preserve for a long time and light weight and high strength, high rigidity. It can extensively be suitable for purposes to industry purposes such as automobile and airborne vehicles from moving and lying fallow.

Claims (10)

1. compositions of thermosetting resin is to be 5 * 10 50 ℃ viscosity ¹～1 * 10 ⁴Pasec and under 120 ℃ atmosphere, reach 1 * 10 with interior at 1000 seconds or its ⁶The compositions of thermosetting resin of Pasec, wherein, after 30 ℃ were placed for 3 weeks 50 ℃ 2 times of viscosity increases or below it.

2. compositions of thermosetting resin according to claim 1, wherein, compositions of thermosetting resin is a composition epoxy resin.

3. according to claim 1 or 2 described compositions of thermosetting resin, wherein, compositions of thermosetting resin contains the lime carbonate as filler.

4. compositions of thermosetting resin according to claim 3, wherein, with respect to 100 mass parts compositions of thermosetting resin, the content of lime carbonate is 10～300 mass parts.

5. prepreg, it is that supporting material is soaked into any described compositions of thermosetting resin in the claim 1～4 and forms.

6. prepreg according to claim 5, wherein, the fiber that constitutes supporting material is a carbon fiber.

7. prepreg according to claim 5, wherein, the fiber that constitutes supporting material is a glass fibre.

8. according to any described prepreg in the claim 5～7, wherein, the volume content of the compositions of thermosetting resin in the prepreg is smaller or equal to 45 volume %.

9. the manufacture method of fibre reinforced composites wherein, is placed according to any described prepreg in the claim 6～8 in shaping dies, and close die heats, pressurizes and is shaped.

10. the manufacture method of fibre reinforced composites according to claim 9, wherein, shaping dies is the shaping dies with common edge structure.

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